JP6652566B2 - Composite with transparent electrode, transfer film, method for manufacturing composite with transparent electrode, and capacitance input device - Google Patents

Description

  The present invention relates to a composite with a transparent electrode, a transfer film, a method for producing the composite with a transparent electrode, and a capacitance-type input device.

Electronic devices such as mobile phones, car navigation systems, personal computers, ticket vending machines, and bank terminals have recently been provided with a liquid crystal display device having a touch panel type input device, and an image or the like displayed on the liquid crystal display device is displayed with a finger or a touch pen. There is an electronic device that can input a desired instruction by touching the electronic device.
The input device (touch panel) includes a resistive type, a capacitive type, and the like.
The capacitance-type input device has an advantage that a transparent conductive film may be simply formed on one base material. In such a capacitance-type input device, for example, when a finger or the like contacts an input surface of the capacitance-type input device by extending a transparent electrode pattern in a direction intersecting with each other, the capacitance between the electrodes is reduced. There is a type that detects a change and detects an input position (for example, see Patent Document 1).

  Patent Literature 1 discloses a transparent electrode pattern, a second curable transparent resin layer disposed adjacent to the transparent electrode pattern, and a first cured resin layer disposed adjacent to the second curable transparent resin layer. The second curable transparent resin layer has a higher refractive index than the first curable transparent resin layer, and the second curable transparent resin layer has a refractive index of 1. A transparent laminate of 6 or more is described. In Patent Document 1, a transparent film having a refractive index of 1.6 to 1.78 and a thickness of 55 to 110 nm is further provided on the side of the transparent electrode pattern opposite to the side on which the second curable transparent resin layer is formed. Is stated to be preferred. According to Patent Document 1, the refractive index difference between the transparent electrode pattern (preferably, indium tin oxide; ITO) and the second curable transparent resin layer, and the second curable transparent resin layer and the first curable transparent resin layer It is described that by reducing the difference in the refractive index of the resin layer, light reflection is reduced, the transparent electrode pattern becomes less visible, and visibility can be improved.

  Patent Document 2 discloses a hard coat layer having a refractive index of 1.60 or more and 1.70 or less and a high refractive index layer having a thickness of 25 nm or more and 35 nm or less on one or both surfaces of a transparent film substrate. A transparent conductive film having a low refractive index layer having a thickness of 40 nm to 50 nm and a transparent conductive layer having a thickness of 40 nm to 50 nm in this order is described. According to Patent Literature 2, with this configuration, it is possible to suppress the difference in visibility between the pattern forming portion and the pattern opening even when the transparent conductive layer is patterned, while suppressing the generation of color. It is stated that a film is obtained.

Patent Document 3 discloses a touch panel in which an undercoat layer containing fine particles a, a high refractive index layer containing fine particles b, and a low refractive index layer containing fine particles c are laminated in this order on a light-transmitting substrate. A hard coat film, wherein the fine particles a, the fine particles b and the fine particles c each have an average particle diameter satisfying the following formula:
The average particle diameter of the fine particles a> the average particle diameter of the fine particles b> the average particle diameter of the fine particles c is described. According to Patent Literature 3, it is described that, with this configuration, the adhesion between the high refractive index layer and the low refractive index layer is extremely excellent, and the film strength is also excellent.

Patent Document 4 discloses a transparent conductive film in which a transparent conductive wiring film is formed on a glass substrate and a dielectric optical multilayer film in which the transmittance in a portion where the wiring film exists and the transmittance in a portion where the wiring film does not exist is equal. A glass substrate with a wiring film is described. Table 1 of Patent Document 4 shows that six layers of ITO wiring pattern / SiO ₂ / Nb ₂ O ₅ / SiO ₂ / Nb ₂ O ₅ / SiO ₂ are formed on soda lime glass (the part without the ITO wiring pattern is five layers). ) Is described. According to Patent Literature 4, with this configuration, when a portion having a wiring pattern and a portion having no wiring pattern are compared in the visible light region, the difference between the transmittance and the reflectance is small and almost the same. Therefore, it is described that not only the drawback of the prior art but that the wiring pattern can be seen is solved, but also a neutral color tone can be realized.

JP 2014-108541 A JP 2014-106779 A JP-A-2005-99538 JP 2010-86684 A JP 2004-50734 A

  The method of providing a high refractive index layer between a substrate and a transparent electrode pattern described in Patent Literature 1 is excellent in concealing properties of the transparent electrode pattern, but lowers the production cost when forming the transparent electrode pattern, Improvements were needed. Therefore, even if a transparent film with a high refractive index is not used on the substrate side of the transparent electrode pattern, a new high refractive index layer is provided on the side opposite to the substrate of the transparent electrode pattern. There is a demand for providing a composite with a transparent electrode having a simple layer configuration and excellent in concealing properties of a transparent electrode pattern.

The present inventors have studied to improve the concealability of the transparent electrode pattern with a novel layer configuration. As a result, the layer configuration is different between a case where a transparent film having a high refractive index is provided on the substrate side of the transparent conductive pattern and a case where a transparent film having a high refractive index is provided on the side opposite to the substrate. It was found that it is better that the design of the preferable refractive index and the range of the thickness is different from those of the described high refractive index layer and low refractive index layer.
Further, in the configuration of ITO wiring pattern / SiO ₂ / Nb ₂ O ₅ / SiO ₂ / Nb ₂ O ₅ / SiO ₂ described in Table 1 of Patent Document 4, the light reflected from the base material surface other than the transparent electrode pattern is used. It has been found that thickness unevenness (uneven thickness) caused by a thin layer for adjusting the refractive index, that is, unevenness caused by the optical adjustment member occurs.

  Further, even when the concealing property of the transparent electrode pattern is improved by a new lamination order, it is still required to provide the hard coat characteristics described in Patent Documents 2 and 3.

The present invention has been made in view of the above circumstances. The problem to be solved by the present invention is that, even if a transparent film having a high refractive index is not used on the substrate side of the transparent electrode pattern, the transparent electrode pattern has excellent concealing properties and can reduce unevenness caused by the optical adjustment member. Another object of the present invention is to provide a composite with a transparent electrode having excellent pencil hardness.
The problem to be solved by the present invention is that, even if a transparent film having a high refractive index is not used on the substrate side of the transparent electrode pattern, the transparent electrode pattern has excellent concealing properties and can reduce unevenness caused by the optical adjustment member. Another object of the present invention is to provide a transfer film used in a method for producing a composite with a transparent electrode having excellent pencil hardness.
The problem to be solved by the present invention is that, even if a transparent film having a high refractive index is not used on the substrate side of the transparent electrode pattern, the transparent electrode pattern has excellent concealing properties and can reduce unevenness caused by the optical adjustment member. Another object of the present invention is to provide a method for producing a composite with a transparent electrode having excellent pencil hardness.
The problem to be solved by the present invention is that, even if a transparent film having a high refractive index is not used on the substrate side of the transparent electrode pattern, the transparent electrode pattern has excellent concealing properties and can reduce unevenness caused by the optical adjustment member. Another object of the present invention is to provide a capacitive input device including a composite with a transparent electrode having excellent pencil hardness.

  In order to solve the above-mentioned problems, the present inventors have intensively studied. As a result, in a composite with a transparent electrode having a base material, a transparent electrode pattern, an optical adjustment member and a transparent protective layer in this order, the specific thickness and refractive index of the low refractive index layer and the high refractive index layer included in the optical adjustment member are determined. By designing the refractive index to be in a specific range, excellent transparency of the transparent electrode pattern and reduction of unevenness caused by the optical adjustment member can be achieved without using a transparent film with a high refractive index on the substrate side of the transparent electrode pattern. It was found that they had excellent pencil hardness.

  This new layer configuration was a layer configuration that could not be assumed by the ordinary design of those skilled in the art. For example, Patent Literature 3 discloses a laminate in which a transparent substrate is bonded via a transparent adhesive layer to a surface of a hard coat film for a touch panel on which a low refractive index layer and a conductive layer are not formed. It is described as good. Patent Document 3 does not disclose or suggest that a transparent substrate is bonded to the surface of the hard coat film for a touch panel on which the low refractive index layer and the conductive layer are formed. The hard coat film for the touch panel is, as described in Yano Keizai Co., Ltd.'s “Capacitance Touch Panel / Member Market Survey Results 2015”, etc., in the touch panel field on the side that becomes the conductive layer base material. Generally, it is a hard coat film. Therefore, laminating a transparent substrate on the conductive layer side of the hard coat film for a touch panel of Patent Document 3 is a layer configuration that cannot be assumed by a normal design of a person skilled in the art.

  In a field other than the composite with a transparent electrode, Patent Document 5 discloses a transfer film in which an anti-reflection transfer film is provided on the surface of a base film, wherein the anti-reflection transfer film has at least a first refraction layer. , A second refraction layer, and a third refraction layer, and each layer is laminated on the surface of the base film in the order described, and the first refraction layer, the second refraction layer, and the third refraction layer are visible. A transfer film in which the light refractive index decreases in the order of the second refractive layer, the third refractive layer, and the first refractive layer is described. The transfer film in which three layers having different refractive indices described in Patent Document 5 are laminated is transferred to glass or acrylic resin to prevent reflection at the glass-air interface. Because of the difference, the design of the refractive index and the thickness was different.

The present invention, which is specific means for solving the above problems, and preferred embodiments of the present invention are as follows.
[1] A composite with a transparent electrode having a substrate, a transparent electrode pattern, an optical adjustment member, and a transparent protective layer in this order,
The optical adjustment member has at least one low-refractive-index layer, which is an odd-numbered layer from the transparent electrode pattern side, and at least one high-refractive-index layer, which is an even-numbered layer from the transparent electrode pattern side. And
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
A composite with a transparent electrode, wherein each of the low refractive index layer and the high refractive index layer has a thickness of 5 to 80 nm.
[2] In the composite with a transparent electrode according to [1], the substrate and the transparent electrode pattern are preferably disposed directly or via a transparent film having a refractive index of 1.46 to 1.58.
[3] In the composite with a transparent electrode according to [1] or [2], the optical adjustment member preferably has one low refractive index layer and one high refractive index layer.
[4] In the composite with a transparent electrode according to any one of [1] to [3], the low refractive index layer preferably has a refractive index of 1.25 to 1.53.
[5] In the composite with a transparent electrode according to any one of [1] to [4], the high refractive index layer preferably has a refractive index of 1.60 to 2.00.
[6] In the composite with a transparent electrode according to any one of [1] to [5], the high refractive index layer preferably contains 10 to 95% by mass of metal oxide particles.
[7] In the composite with a transparent electrode according to any one of [1] to [6], the optical adjustment member and the transparent protective layer are preferably formed by transfer.
[8] In the composite with a transparent electrode according to any one of [1] to [7], the low refractive index layer and the high refractive index layer are preferably transparent resin layers.
[9] A transfer film having a temporary support, a transparent protective layer, an optical adjustment member, and a protective film in this order,
The optical adjustment member has at least one layer each of a low-refractive-index layer disposed odd-numbered from the protective film side and a high-refractive-index layer disposed evenly from the protective film side,
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
A transfer film wherein the low refractive index layer and the high refractive index layer each have a thickness of 5 to 80 nm.
[10] In the transfer film according to [9], the low refractive index layer and the high refractive index layer are curable transparent resin layers containing a polymerizable compound, and the curable transparent resin layer is not cured. preferable.
[11] A laminating step of laminating the optical adjustment member and the transparent protective layer in this order on the transparent electrode pattern arranged on the base material,
The optical adjustment member has at least one layer each of a low-refractive-index layer arranged oddly from the transparent electrode pattern side and a high-refractive-index layer arranged evenly from the transparent electrode pattern side,
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
A method for producing a composite with a transparent electrode, wherein each of the low refractive index layer and the high refractive index layer has a thickness of 5 to 80 nm.
[12] In the method for producing a composite with a transparent electrode according to [11], the substrate and the transparent electrode pattern are preferably disposed directly or via a transparent film having a refractive index of 1.46 to 1.58.
[13] In the method for producing a composite with a transparent electrode according to [11] or [12], the laminating step may be performed on the transparent electrode pattern disposed on the base material according to [9] or [10]. The step of transferring the optical adjustment member and the transparent protective layer from the transfer film described above is preferable.
[14] The method for producing a composite with a transparent electrode according to any one of [11] to [13], wherein the low refractive index layer and the high refractive index layer are curable transparent resin layers containing a polymerizable compound. Preferably, the curable transparent resin layer before being laminated on the transparent electrode pattern is uncured.
[15] A composite with a transparent electrode produced by the method for producing a composite with a transparent electrode according to any one of [11] to [14].
[16] A capacitive input device including the composite with a transparent electrode according to any one of [1] to [8] and [15].

  According to the present invention, even if a transparent film having a high refractive index is not used on the substrate side of the transparent electrode pattern, excellent concealing properties of the transparent electrode pattern can be obtained, unevenness due to the optical adjustment member can be reduced, and pencil hardness can be reduced. An excellent composite with a transparent electrode can be provided.

1 is a schematic cross-sectional view illustrating an example of the configuration of a capacitance-type input device according to the present invention. It is explanatory drawing which shows an example of the base material in this invention. It is explanatory drawing which shows an example of the relationship between the transparent electrode pattern and non-pattern area | region in this invention. It is a top view which shows an example of the base material in which the opening part was formed. FIG. 3 is a top view illustrating an example of a base material on which a mask layer is formed. FIG. 3 is a top view illustrating an example of a base material on which a first transparent electrode pattern is formed. FIG. 4 is a top view illustrating an example of a base material on which first and second transparent electrode patterns are formed. It is a top view which shows an example of the base material in which the electroconductive element different from the 1st and 2nd transparent electrode pattern was formed. FIG. 4 is a schematic sectional view showing another example of the configuration of the capacitance-type input device of the present invention. It is explanatory drawing which shows an example of the taper shape of the edge part of a transparent electrode pattern. 1 is a schematic cross-sectional view illustrating an example of the configuration of a composite with a transparent electrode according to the present invention. FIG. 1 is a schematic sectional view showing an example of the configuration of a transfer film of the present invention. FIG. 4 is a top view illustrating another example of the configuration of the capacitance-type input device of the present invention, showing a mode including a terminal portion (terminal portion) of a routing wiring that has been pattern-exposed and is not covered with a transparent protective layer. It is a schematic diagram showing an example of a state before the transfer film of the present invention having a transparent protective layer and an optical adjustment member is laminated on a transparent electrode pattern of a capacitive input device by lamination and cured by exposure or the like. . It is the schematic which shows an example of the desired pattern in which the transparent protective layer and the optical adjustment member were hardened. FIG. 2 is a schematic cross-sectional view showing an example of a transparent electrode pattern disposed on a substrate, which is used in the method for producing a composite with a transparent electrode of the present invention. FIG. 4 is a schematic sectional view showing another example of the configuration of the composite with a transparent electrode of the present invention. FIG. 4 is a schematic sectional view showing another example of the configuration of the composite with a transparent electrode of the present invention.

  Hereinafter, the composite with a transparent electrode, the transfer film, the method for producing the composite with a transparent electrode, and the capacitance-type input device of the present invention will be described. The description of the components described below may be made based on typical embodiments and specific examples of the present invention, but the present invention is not limited to the embodiments and specific examples. In this specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit and an upper limit.

[Composite with transparent electrode]
The composite with a transparent electrode of the present invention is a composite with a transparent electrode having a substrate, a transparent electrode pattern, an optical adjustment member and a transparent protective layer in this order,
The optical adjustment member has at least one low-refractive-index layer, which is an odd-numbered layer from the transparent electrode pattern side, and at least one high-refractive-index layer, which is an even-numbered layer from the transparent electrode pattern side. And
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The thickness of each of the low refractive index layer and the high refractive index layer is 5 to 80 nm.
With this configuration, the composite with a transparent electrode of the present invention is excellent in concealing properties of the transparent electrode pattern without using a high refractive index transparent film on the substrate side of the transparent electrode pattern, and is caused by the optical adjustment member. It can reduce unevenness and has excellent pencil hardness.

The composite with a transparent electrode of the present invention is a composite with a transparent electrode having a conventional layer configuration in which an optical adjustment member and a transparent protective layer are formed by transfer, and a transparent conductive pattern is formed on a substrate with an optical adjustment member. Is more preferable than the method for producing In particular, the optical adjustment member is not damaged during the formation of the transparent conductive layer, the optical adjustment member is not damaged due to the etching solution during the patterning of the transparent conductive layer, and the adhesion between the optical adjustment member and the transparent conductive pattern is prevented. It is preferable from the viewpoint that the property is also improved. Also, even if a transparent film having a high refractive index is not used on the substrate side of the transparent electrode pattern, the transparent electrode pattern is excellent in concealing properties, can reduce unevenness caused by the optical adjustment member, and has excellent pencil hardness. It is also preferable from the viewpoint that the attached composite can be easily produced with high productivity. Further, it is preferable that the optical adjustment member and the transparent protective layer are formed by transfer from the viewpoint of easily reducing the occurrence of unevenness (thickness unevenness; thickness unevenness is synonymous with uneven thickness) due to the optical adjustment member.
Unless otherwise specified, the refractive index in this specification indicates a refractive index at a wavelength of 550 nm.
In addition, in this specification, transparent means that the average transmittance of visible light having a wavelength of 400 nm to 700 nm is 80% or more. Therefore, a transparent layer refers to a layer having an average transmittance of visible light of a wavelength of 400 nm to 700 nm of 80% or more. The average transmittance of the transparent layer for visible light having a wavelength of 400 nm to 700 nm is preferably 90% or more.
The average transmittance of visible light having a wavelength of 400 nm to 700 nm of the transfer film of the invention or the transparent layer of the transfer film is measured using a spectrophotometer U-3310 manufactured by Hitachi, Ltd.
Hereinafter, preferred embodiments of the composite with a transparent electrode of the present invention will be described.

<Composition of composite with transparent electrode>
The composite with a transparent electrode of the present invention is a composite with a transparent electrode having a substrate, a transparent electrode pattern, an optical adjustment member and a transparent protective layer in this order, wherein the optical adjustment member is an odd number from the transparent electrode pattern side. It has at least one low-refractive-index layer as a disposed layer and at least one high-refractive-index layer as an even-numbered layer from the transparent electrode pattern side.
FIG. 11 shows an example of the configuration of the composite with a transparent electrode of the present invention. The composite with a transparent electrode of the present invention shown in FIG. 11 has a substrate 1, a transparent electrode pattern 4, an optical adjustment member 12, and a transparent protective layer 7 in this order, and the substrate 1 and the transparent electrode pattern 4 are bent. The transparent film 11 having a ratio of 1.46 to 1.58 is interposed. Although the details of the optical adjustment member 12 are not shown in FIG. 11, the optical adjustment member 12 having the configuration shown in FIGS. 17 and 18 can also be employed in FIG.
FIG. 17 shows another example of the configuration of the composite with a transparent electrode of the present invention. The composite with a transparent electrode of the present invention shown in FIG. 17 has a substrate 1, a transparent electrode pattern 4, an optical adjustment member 12, and a transparent protective layer 7 in this order, and the substrate 1 and the transparent electrode pattern 4 are bent. A low refractive index layer 12A, which is a layer in which the optical adjustment member 12 is disposed at an odd number from the transparent electrode pattern side, and an even number from the transparent electrode pattern side, wherein the optical adjustment member 12 is disposed via the transparent film 11 having a ratio of 1.46 to 1.58. And a high-refractive-index layer 12B which is the second layer.
FIG. 18 shows another example of the configuration of the composite with a transparent electrode of the present invention. The composite with a transparent electrode of the present invention shown in FIG. 18 has a substrate 1, a transparent electrode pattern 4, an optical adjustment member 12, and a transparent protective layer 7 in this order, and the substrate 1 and the transparent electrode pattern 4 are directly The optical adjustment member 12 is disposed in direct contact with the low-refractive-index layer 12 </ b> A, which is an odd-numbered layer from the transparent electrode pattern side, and three even-numbered layers from the transparent electrode pattern side. There are two high refractive index layers 12B.

In the composite with a transparent electrode of the present invention, the substrate and the transparent electrode pattern may be directly disposed, or may be disposed via a transparent film. FIGS. 11 and 17 show an embodiment in which the substrate 1 and the transparent electrode pattern 4 are arranged via the transparent film 11 having a refractive index of 1.46 to 1.58. On the other hand, FIG. 18 shows an aspect in which the substrate 1 and the transparent electrode pattern 4 are directly arranged.
It is preferable that the substrate 1 and the transparent electrode pattern 4 are directly arranged from the viewpoint of reducing the reflectance of the transparent electrode pattern and the concealing property of the transparent electrode pattern.

  The number of low-refractive-index layers and high-refractive-index layers of the optical adjustment member is not particularly limited, but is preferably independently 1 to 5 layers, and more preferably independently 1 to 3 layers. It is particularly preferable that each has one or two layers independently, and it is particularly preferable that each has one layer from the viewpoint of processes such as reduction in manufacturing cost and improvement in manufacturing suitability. In the composite with a transparent electrode of the present invention, the optical adjustment member preferably has one low refractive index layer and one high refractive index layer.

As shown in FIG. 11, the composite with a transparent electrode of the present invention has an in-plane region 21 where a substrate 1, a transparent film 11, a transparent electrode pattern 4, an optical adjustment member 12, and a transparent protective layer 7 are laminated in this order. It is preferred to have. In FIG. 11, in addition to the above-described region, the above-described composite with a transparent electrode has a region 22 (that is, a transparent region) in which the base material 1, the transparent film 11, the optical adjustment member 12, and the transparent protective layer 7 are laminated in this order. It is shown that it includes a non-pattern region 22) where no electrode pattern is formed.
The in-plane direction means a direction substantially parallel to a plane parallel to the substrate of the composite with a transparent electrode. Therefore, to include in the plane a region in which the transparent electrode pattern 4, the optical adjustment member 12, and the transparent protective layer 7 are laminated in this order means that the transparent electrode pattern 4, the optical adjustment member 12, and the transparent protective layer 7 are laminated in this order. This means that the orthographic projection of the region to the plane parallel to the substrate of the composite with a transparent electrode is present in the plane parallel to the substrate of the composite with a transparent electrode.

  Here, when the composite with a transparent electrode of the present invention is used for a capacitance-type input device to be described later, the transparent electrode pattern and the first transparent electrode pattern and the second transparent electrode pattern are arranged in two directions substantially orthogonal to the row direction and the column direction, respectively. It may be provided as two transparent electrode patterns (for example, see FIG. 3). For example, in the configuration of FIG. 3, the transparent electrode pattern in the composite with a transparent electrode of the present invention may be the second transparent electrode pattern 4 or the pad portion 3 a of the first transparent electrode pattern 3. In other words, in the following description of the composite with a transparent electrode of the present invention, the sign of the transparent electrode pattern may be represented by “4”, but the transparent electrode pattern in the composite with a transparent electrode of the present invention is The present invention is not limited to the use for the second transparent electrode pattern 4 in the capacitive input device of the present invention, and may be used, for example, as the pad portion 3a of the first transparent electrode pattern 3.

The composite with a transparent electrode of the present invention preferably includes a non-pattern region where the above-mentioned transparent electrode pattern is not formed. In the present specification, the non-pattern region means a region where the transparent electrode pattern 4 is not formed.
FIG. 11 shows an embodiment in which the composite with a transparent electrode of the present invention includes the non-patterned region 22.
The composite with a transparent electrode of the present invention includes an in-plane region in which the aforementioned base material and the aforementioned optical adjustment member are laminated in this order on at least a part of the non-pattern region 22 where the aforementioned transparent electrode pattern is not formed. Is preferably included.
However, other members of the non-pattern region 22 described above may be provided with other members at any positions as long as they do not contradict the spirit of the present invention. For example, a composite with a transparent electrode of the present invention will be described later. When used for a capacitance-type input device, the mask layer 2, the insulating layer 5, another conductive element 6, and the like in FIG. 1 can be laminated.

The end of the above-mentioned transparent electrode pattern 4 is not particularly limited in its shape, and may have a tapered shape as shown in FIG. 11. It may have a tapered shape wider than the surface on the side opposite to the substrate.
Here, when the end of the transparent electrode pattern is tapered, the angle of the end of the transparent electrode pattern (hereinafter, also referred to as a taper angle) is preferably 30 ° or less, and 0.1 to 15 °. More preferably, and particularly preferably 0.5 to 5 °.
The method for measuring the taper angle in the present specification can be obtained by taking a micrograph of the end of the above-described transparent electrode pattern, approximating the tapered portion of the micrograph to a triangle, and directly measuring the taper angle. .
FIG. 10 shows an example in which the end of the transparent electrode pattern has a tapered shape. The triangle approximating the tapered portion in FIG. 10 has a bottom surface of 800 nm, a height (a thickness at an upper bottom portion substantially parallel to the bottom surface) of 40 nm, and a taper angle α at this time of about 3 °. The bottom surface of the triangle approximating the tapered portion is preferably 10 to 3000 nm, more preferably 100 to 1500 nm, and particularly preferably 300 to 1000 nm.
The preferred range of the height of the triangle approximating the tapered portion is the same as the preferred range of the thickness of the transparent electrode pattern.

The composite with a transparent electrode of the present invention preferably includes a region where the above-mentioned transparent electrode pattern and the above-mentioned optical adjustment member are adjacent to each other.
In FIG. 11, in the region 21 where the above-mentioned transparent electrode pattern, the above-mentioned optical adjustment member and the transparent protective layer are laminated in this order, the above-mentioned transparent electrode pattern, the above-mentioned optical adjustment member and the transparent protective layer are adjacent to each other. One embodiment is shown.

Further, in the composite with a transparent electrode of the present invention, it is preferable that both the transparent electrode pattern and the non-pattern region 22 where the transparent electrode pattern is not formed are continuously covered by the optical adjustment member.
Here, “continuously” means that the optical adjustment member is not a pattern film but a continuous film. That is, it is preferable that the optical adjustment member has no opening from the viewpoint of making the transparent electrode pattern less visible.
Further, it is preferable that the above-mentioned transparent electrode pattern and the above-mentioned non-pattern region 22 are directly covered with the optical adjustment member, rather than being covered with another layer. The “other layer” in the case of being coated via another layer includes an insulating layer 5 included in a capacitance-type input device of the present invention described later and a capacitance-type input device of the present invention described later. As described above, a second-layer transparent electrode pattern in the case where two or more transparent electrode patterns are included can be exemplified.
FIG. 11 shows a mode in which the above-described optical adjustment members 12 are stacked. The above-described optical adjustment member 12 is laminated over a region on the transparent film 11 where the transparent electrode pattern 4 is not laminated and a region where the transparent electrode pattern 4 is laminated. That is, the above-described optical adjustment member 12 is adjacent to the above-described transparent film 11, and the above-described optical adjustment member 12 is adjacent to the transparent electrode pattern 4.
When the end of the transparent electrode pattern 4 has a tapered shape, it is preferable that the above-described optical adjustment member 12 is laminated along the tapered shape (with the same inclination as the taper angle).

  FIG. 11 shows an embodiment in which the transparent protective layer 7 is laminated on the surface of the optical adjustment member 12 opposite to the surface on which the transparent electrode pattern is formed. The shape of the transparent protective layer 7 is not particularly limited, but is preferably a continuous film covering the optical adjustment member 12.

<Material of composite with transparent electrode>
(Base material)
In the composite with a transparent electrode of the present invention, the substrate is preferably a glass substrate or a film substrate, and more preferably a film substrate. Further, the substrate is preferably a transparent substrate. That is, the above-mentioned substrate is preferably a transparent film substrate.
The refractive index of the substrate is particularly preferably from 1.5 to 1.52.
The base material may be composed of a glass base material, and as the glass base material, a tempered glass represented by gorilla glass of Corning or the like can be used.
Further, as the transparent substrate, the materials used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be preferably used.
When a film substrate is used as the above-mentioned substrate, it is more preferable to use one having no optical distortion or high transparency. Specifically, polyethylene terephthalate (PET), polyethylene naphthalate , Polycarbonate, triacetyl cellulose, and cycloolefin polymers.
In the composite with a transparent electrode, the transparent electrode pattern is preferably a transparent electrode pattern formed on a transparent film substrate.
It is also preferable that the composite with a transparent electrode has a configuration in which a transparent electrode pattern, an optical adjustment member, and a transparent protective layer are respectively provided on both surfaces of the substrate. In this case, the composite with a transparent electrode is preferably used as a film sensor.

(Transparent electrode pattern)
The transparent electrode pattern in the composite with a transparent electrode of the present invention preferably has a refractive index of 1.75 to 2.1.
The material of the above-mentioned transparent electrode pattern is not particularly limited, and a known material can be used. Examples of the material of the transparent electrode pattern include a metal film and a transparent and conductive metal oxide film such as ITO and IZO (Indium Zinc Oxide). Examples of the metal film and the metal oxide film include metal films such as Al, Zn, Cu, Fe, Ni, Cr, and Mo; and metal oxide films such as ITO and SiO ₂ . At this time, the thickness of the transparent electrode pattern can be 10 to 200 nm.
When the amorphous ITO film is converted into a polycrystalline ITO film by firing, the electric resistance can be reduced.
In addition, there is no particular limitation on the method for manufacturing the transparent electrode pattern. For example, as described later, the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described later are formed of a photosensitive film having a photocurable resin layer using conductive fibers. It can also be manufactured using. In addition, when forming the first transparent electrode pattern or the like by ITO or the like, paragraphs 0014 to 0016 of Japanese Patent No. 4506785 can be referred to.
The transparent electrode pattern is preferably an ITO film.
In the composite with a transparent electrode of the present invention, the transparent electrode pattern is more preferably an ITO film having a refractive index of 1.75 to 2.1.

(Optical adjustment member)
The composite with a transparent electrode of the present invention has an optical adjustment member,
The optical adjustment member has at least one low-refractive-index layer, which is an odd-numbered layer from the transparent electrode pattern side, and at least one high-refractive-index layer, which is an even-numbered layer from the transparent electrode pattern side. And
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The thickness of each of the low refractive index layer and the high refractive index layer is 5 to 80 nm.

In the composite with a transparent electrode of the present invention, the difference in the refractive index between the low refractive index layer and the directly adjacent high refractive index layer is 0.05 or more.
The difference in the refractive index between the low refractive index layer and the directly adjacent high refractive index layer is preferably 0.05 to 0.50, and more preferably 0.05 to 0.30.

  In the composite with a transparent electrode of the present invention, the refractive index of the low refractive index layer is preferably from 1.25 to 1.53, more preferably from 1.30 to 1.53, and more preferably from 1.35 to 1. .53 is particularly preferred.

In the composite with a transparent electrode of the present invention, the refractive index of the high refractive index layer is 2.10 or less. As the refractive index increases, it is preferable to reduce the thickness of the high refractive index layer from the viewpoint of improving the concealability of the transparent electrode pattern. On the other hand, the thickness of the high-refractive-index layer does not become too thin because the refractive index of 2.10 or less, which is lower than the refractive index (n = 2.33) of niobium oxide, is not too thin. The problem that unevenness due to an optical adjustment member other than the transparent electrode pattern occurs in the reflected light can be improved simultaneously with the concealing property of the transparent electrode pattern.
In the composite with a transparent electrode of the present invention, the refractive index of the high refractive index layer is preferably from 1.60 to 2.00, more preferably from 1.60 to 1.80, and from 1.60 to 1.80. .75 is particularly preferred.
When the refractive index of the transparent electrode pattern exceeds 2.0 as in the case of oxides of In and Zn, the refractive index of the high refractive index layer of the optical adjustment member is 1.7 or more and 1.85 or less. Preferably, there is.

In the composite with a transparent electrode of the present invention, the thickness of each of the low refractive index layer and the high refractive index layer is 5 to 80 nm. The thickness of the low refractive index layer and the high refractive index layer of the optical adjustment member is more preferably 10 to 75 nm, and particularly preferably 15 to 70 nm.
The thicknesses of the low refractive index layer and the high refractive index layer of the optical adjustment member are determined by the method described in Examples described later.

The low refractive index layer and the high refractive index layer of the optical adjustment member may be a transparent resin film or an inorganic film. The composite with a transparent electrode of the present invention is such that the low-refractive index layer and the high-refractive index layer are transparent resin layers, compared to an inorganic film formed by evaporation or the like, lowering production costs, improving production suitability, etc. Preferred from a process point of view. In particular, it is more preferable that the high refractive index layer is a transparent resin layer containing a metal oxide.
As the inorganic film, the inorganic films used in JP-A-2010-86684, JP-A-2010-152809, JP-A-2010-257492, and the like can be used, which are described in these documents. It is preferable to use an inorganic film having a laminated structure of a low refractive index material and a high refractive index material or an inorganic film of a mixed film of a low refractive index material and a high refractive index material from the viewpoint of controlling the refractive index. As the low refractive index material and the high refractive index material, the materials used in the above-mentioned JP-A-2010-86684, JP-A-2010-152809 and JP-A-2010-257492 can be preferably used. Is incorporated herein by reference.
The inorganic film includes a SiO _x film (x is preferably 1.5 to 2.5, more preferably 1.5 to 2.0, particularly preferably 1.7 to 2.0), a Y ₂ O ₃ film, and a ZrO film. _Two films may be used. The inorganic film may be a film formed by vapor deposition, a film formed by sputtering, or a film formed by another method. From the viewpoint of the above, a film formed by sputtering is more preferable.

The transparent resin film may be a curable transparent resin layer or a non-curable transparent resin layer, but the curable transparent resin layer is preferably a composite with a transparent electrode (and It is preferable from the viewpoint of enhancing the photolithography of the transfer film). That is, in the composite with a transparent electrode of the present invention, the low refractive index layer and the high refractive index layer are preferably curable transparent resin layers containing a polymerizable compound. It is preferable that the curable transparent resin layer is a cured film in the final form. In the present specification, “the curable transparent resin layer is not cured” means that the consumption rate of the curable group contained in the curable transparent resin layer is less than 10%. For example, if the unsaturated double bond consumption rate of the unsaturated double bond group is less than 10%, it becomes an uncured curable transparent resin layer. The fact that the curable transparent resin layer is a cured film means that the curable group contained in the curable transparent resin layer has a consumption rate of 10% or more. The consumption rate of the curable group of the cured film is preferably 90% or more.
When the low-refractive-index layer and the high-refractive-index layer of the optical adjustment member are curable transparent resin layers, they may be thermosetting, photocurable, thermosetting and photocurable. Is also good. Among them, it is preferable that the low refractive index layer and the high refractive index layer of the optical adjustment member are at least thermosetting from the viewpoint that the film can be heat-cured after transfer to impart film reliability and wet heat durability. Further, it is more preferable that the film is photocurable from the viewpoint that the film can be easily formed by photocuring after transfer, and that the film can be thermally cured after film formation to impart reliability and wet heat durability to the film.
The low refractive index layer and the high refractive index layer of the optical adjustment member preferably contain a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.
The low refractive index layer and the high refractive index layer of the optical adjustment member may be a negative type material or a positive type material.
When the low refractive index layer and the high refractive index layer of the optical adjustment member are negative materials, the low refractive index layer and the high refractive index layer of the optical adjustment member include a binder polymer (preferably an alkali-soluble resin) and a photopolymerizable polymer. It is preferable to include a compound and a photopolymerization initiator. More preferably, the high refractive index layer of the optical adjustment member contains metal oxide particles. Further, an additive or the like is used, but is not limited thereto.

There is no particular limitation on the method of controlling the refractive index of the low refractive index layer and the high refractive index layer of the optical adjustment member. Or a complex of a metal salt and a polymer.
In the composite with a transparent electrode of the present invention, the high refractive index layer preferably contains metal oxide particles. The high refractive index layer preferably contains 10 to 95% by mass of metal oxide particles, more preferably 40 to 95% by mass, particularly preferably 55 to 95% by mass, and 62 to 90% by mass. %, More preferably 65 to 90% by mass.

  Further, an additive may be used for the low refractive index layer and the high refractive index layer of the optical adjustment member. Examples of the additives include surfactants described in paragraph 0017 of Japanese Patent No. 4502784, paragraphs 0060 to 0071 of JP-A-2009-237362, and thermal polymerization described in paragraph 0018 of Japanese Patent No. 4502784. Inhibitors and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

  The details of the materials of the low refractive index layer and the high refractive index layer of the optical adjustment member will be described later in the method of manufacturing a transfer film.

(Transparent protective layer)
The transparent protective layer is preferably a transparent resin layer, and more preferably a curable transparent resin layer.
When the transparent protective layer is a curable transparent resin layer, it may be thermosetting, photocurable, thermosetting and photocurable. Among them, it is preferable that the transparent protective layer is at least thermosetting, from the viewpoint of imparting the reliability of the film by thermosetting after transfer. It is more preferable from the viewpoint that it is easy to form a film and that the film can be thermally cured after the film formation to give the film reliability.

The transparent protective layer preferably contains a surfactant containing a fluorine atom in an amount of 0.01 to 0.5% by mass based on the solid content of the transparent protective layer. When the transparent protective layer contains a surfactant containing a fluorine atom, the conventional effect of the surfactant "reducing the surface tension and smoothing the surface of the wet coating film after application" is obtained. Can be In addition, when the transparent protective layer contains a surfactant containing a fluorine atom, when the transparent protective layer is applied and dried, a thin layer of a surfactant containing a fluorine atom is formed on the surface of the transparent protective layer, This serves as a protective layer, and when the optical adjustment member is applied, interlayer mixing with the transparent protective layer can be suppressed. This effect is remarkably obtained by including a surfactant containing 0.01% by mass or more of a fluorine atom with respect to the solid content of the transparent protective layer, and a surfactant containing 0.02% by mass or more of a fluorine atom is contained. This effect can be further remarkably obtained by including the agent.
More preferably, the transparent protective layer contains a surfactant containing a fluorine atom in an amount of 0.02 to 0.5% by mass, more preferably 0.02 to 0.4% by mass, based on the solid content of the transparent protective layer. Particularly preferred. In order to maintain good adhesion between the optical adjustment member and the transparent electrode pattern, it is preferable that a surfactant containing a fluorine atom be contained in an amount of 0.5% by mass or less based on the solid content of the transparent protective layer. It is more preferable that the content is not more than mass%.
Further, when an acrylic resin is selected as the resin of the transparent protective layer and combined with a surfactant containing a fluorine atom, this effect can be more remarkably obtained.
Examples of the surfactant containing a fluorine atom preferably used in the transparent protective layer include, for example, the surfactants described in paragraphs 0017 of Japanese Patent No. 4502784 and paragraphs 0060 to 0071 of JP-A-2009-237362. it can. Further, as the surfactant containing a fluorine atom which is preferably used for the transparent protective layer, a commercially available surfactant containing a fluorine atom can be used. In particular, the following surfactants containing a fluorine atom are preferred.
MegaFac F251, Megafac F253, Megafac F281, Megafac F444, Megafac F477, Megafac F551, Megafac F552, Megafac F553, Megafac F554, Megafac F555, Megafac F556, Mega FAX F557, MegaFac F558, MegaFac F559, MegaFac F560, MegaFac F561, MegaFac F562, MegaFac F563, MegaFac F565, MegaFac F568, MegaFac F569, MegaFac F570, MegaFac F571, MegaFac R40 , Mega Fuck R41, Mega Fuck R43, Mega Fuck R94, Mega Fuck RS55, Mega Fuck RS56, Fuck RS72-K, Megafac RS75, Megafac RS76-E, Megafac RS76-NS, Megafac RS78, mega fuck RS90, mega fuck F780F.
Further, a compound represented by the following formula (3) (weight average molecular weight: 15,000, solid content: 30% by mass, methyl ethyl ketone: 70% by mass) is also preferable and can be used.
Equation (3)

It is preferable that the transparent protective layer contains a binder polymer, a polymerizable compound and a photopolymerization initiator.
The transparent protective layer may be a negative type material or a positive type material.
When the transparent protective layer is a negative-type material, the transparent protective layer preferably contains a binder polymer (preferably an alkali-soluble resin), a photopolymerizable compound, and a photopolymerization initiator. Further, an additive or the like is used, but is not limited thereto.

  The method for controlling the refractive index of the transparent protective layer is not particularly limited, but a transparent protective layer having a desired refractive index may be used alone, or a transparent protective layer to which particles such as metal particles and metal oxide particles are added may be used. Alternatively, a composite of a metal salt and a polymer can be used.

  Further, an additive may be used in the transparent protective layer described above. Examples of the above-mentioned additives include thermal polymerization inhibitors described in paragraph 0018 of Japanese Patent No. 4502784, and other additives described in paragraphs 0058 to 0071 of JP-A-2000-310706.

The thickness of the transparent protective layer may be 1 μm or more from the viewpoint of exhibiting sufficient surface protective ability when forming the transparent protective layer of the capacitive input device using the transparent protective layer and increasing pencil hardness. It is more preferably 1 to 15 μm, particularly preferably 2 to 12 μm, and particularly preferably 3 to 10 μm.
The thickness of the transparent protective layer is determined by the method described in Examples below.

  The refractive index of the transparent protective layer is preferably from 1.45 to 1.59, more preferably from 1.50 to 1.53, particularly preferably from 1.50 to 1.52. .51 to 1.52 is more preferred.

(Transparent film)
When the substrate and the transparent electrode pattern are arranged via the transparent film, the refractive index of the transparent film is not particularly limited. In the composite with a transparent electrode of the present invention, the substrate and the transparent electrode pattern may be arranged via a transparent film having a refractive index of 1.45 or less or a transparent film having a refractive index of 1.59 or more. It is preferable that the electrode pattern is disposed directly or via a transparent film having a refractive index of 1.46 to 1.58 from the viewpoint of reduction in manufacturing cost and improvement in manufacturing suitability. In the composite with a transparent electrode of the present invention, the refractive index of the above-mentioned transparent film is preferably from 1.46 to 1.58, more preferably from 1.5 to 1.53, and more preferably from 1.5 to 1.53. .52, particularly preferably 1.51 to 1.52. Here, the above-mentioned transparent film may have a single-layer structure or a laminated structure of two or more layers. When the above-mentioned transparent film has a laminated structure of two or more layers, the refractive index of the above-mentioned transparent film means the refractive index of all the layers.
The material of the transparent film is not particularly limited, but a material satisfying the range of the refractive index is preferable.

The preferable range of the material of the transparent film and the preferable range of the physical properties such as the refractive index are the same as those of the above-described optical adjustment member.
In the composite with a transparent electrode of the present invention, it is preferable from the viewpoint of optical homogeneity that the above-mentioned transparent film and the above-mentioned optical adjustment member are made of the same material.

In the composite with a transparent electrode of the present invention, the thickness of the above-mentioned transparent film is preferably 55 to 110 nm, more preferably 60 to 110 nm, and particularly preferably 70 to 90 nm.
Here, the above-mentioned transparent film may have a single-layer structure or a laminated structure of two or more layers. When the above-mentioned transparent film has a laminated structure of two or more layers, the thickness of the above-mentioned transparent film means the total thickness of all the layers.

In the composite with a transparent electrode of the present invention, the transparent film is preferably a transparent resin film.
The metal oxide particles, resin (binder) and other additives used in the transparent resin film are not particularly limited as long as they do not depart from the gist of the present invention, and the above-described optical adjustment member in the composite with a transparent electrode of the present invention. The resin used for the above and other additives can be preferably used.
In the composite with a transparent electrode of the present invention, the above-mentioned transparent film may be an inorganic film. As the material used for the inorganic film, the material used for the above-described optical adjustment member in the composite with a transparent electrode of the present invention can be preferably used.

[Method for producing composite with transparent electrode]
The method for producing a composite with a transparent electrode of the present invention has a laminating step of laminating an optical adjustment member and a transparent protective layer in this order on a transparent electrode pattern arranged on a substrate,
The optical adjustment member has at least one layer each of a low-refractive-index layer arranged oddly from the transparent electrode pattern side and a high-refractive-index layer arranged evenly from the transparent electrode pattern side,
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The thickness of each of the low refractive index layer and the high refractive index layer is 5 to 80 nm.
With this configuration, a method for producing a composite with a transparent electrode of the present invention which is excellent in production cost and production suitability is provided. In the method for producing a composite with a transparent electrode according to the present invention, an optical adjustment member and a transparent protective layer are laminated on a transparent conductive pattern. Manufacturing in this order is preferable compared to a conventional method of manufacturing a composite with a transparent electrode having a layer configuration in which a transparent conductive pattern is formed on a substrate with an optical adjustment member. In particular, the optical adjustment member is not damaged when the transparent conductive layer is formed, the optical adjustment member is not damaged by the etching solution when the transparent conductive layer is patterned, and the optical adjustment member and the transparent conductive pattern are in close contact with each other. The performance is also improved. Even if a transparent substrate is laminated on the conductive layer side of the hard coat film for a touch panel disclosed in Japanese Patent Application Laid-Open No. 2015-99538, since the lamination order is different, the advantage of the above-described method for producing a composite with a transparent electrode of the present invention can be obtained. Can not.

<Surface treatment of substrate>
Further, in order to enhance the adhesion of each layer after the lamination in the subsequent transfer step, the non-contact surface of the base material (the input of a finger or the like among the surfaces of the base material constituting the capacitance type input device) is required. A surface treatment can be applied to the surface opposite to the side on which the means is brought into contact. As the above-mentioned surface treatment, it is preferable to carry out a surface treatment using a silane compound (silane coupling treatment). As the silane coupling agent, those having a functional group that interacts with the photosensitive resin are preferable. For example, a silane coupling liquid (0.3 mass% aqueous solution of N-β (aminoethyl) γ-aminopropyltrimethoxysilane, trade name: KBM603, manufactured by Shin-Etsu Chemical Co., Ltd.) is sprayed with a shower for 20 seconds, and pure water shower is performed. Wash. Thereafter, the reaction is preferably performed by heating. A heating tank may be used, or preheating of the laminator may be used, and any of them can promote the reaction.

<Transparent film production>
In the method for producing a composite with a transparent electrode of the present invention, the substrate and the transparent electrode pattern are preferably disposed directly or via a transparent film, and directly or via a transparent film having a refractive index of 1.46 to 1.58. It is more preferable to arrange them. In the case of the composite with a transparent electrode of the present invention, when the substrate and the transparent electrode pattern are arranged via a transparent film having a refractive index of 1.46 to 1.58, a transparent film having a refractive index of 1.46 to 1.58 is formed. The film forming method is not particularly limited, but it is preferable to form the film by transfer or sputtering.
Among them, in the composite with a transparent electrode of the present invention, it is preferable that the transparent film is formed by transferring the transparent curable resin film formed on the temporary support onto the above-described substrate. More preferably, the film is formed by curing after the transfer. As a method of transfer and curing, a photosensitive film is used in the description of the capacitance-type input device of the present invention to be described later, and the above-mentioned transparent protective layer and the above-mentioned optical adjustment member in the method for producing a composite with a transparent electrode are transferred. The method of performing transfer, exposure, development and other steps in the same manner as the above method can be used. In that case, it is preferable to adjust the refractive index of the above-mentioned transparent film to the above-mentioned range by dispersing the above-mentioned metal oxide particles in the photocurable resin layer in the photosensitive film.

On the other hand, when the above-mentioned transparent film is an inorganic film, it is preferably formed by sputtering. That is, in the composite with a transparent electrode of the present invention, it is also preferable that the above-mentioned transparent film is formed by sputtering.
As a sputtering method, a method used in JP-A-2010-86684, JP-A-2010-152809, and JP-A-2010-257492 can be preferably used.

<Film formation of transparent electrode pattern>
The above-mentioned transparent electrode pattern is formed on a base material or a transparent film by using a method for forming a first transparent electrode pattern 3, a second transparent electrode pattern 4, and another conductive element 6, which will be described later. And a method using a photosensitive film is preferable.

<Lamination process>
The method for producing a composite with a transparent electrode of the present invention includes a laminating step of laminating an optical adjustment member and a transparent protective layer in this order on a transparent electrode pattern arranged on a substrate.
The above-mentioned optical adjustment member in the method for manufacturing a composite with a transparent electrode is formed on the above-mentioned substrate or transparent film in the above-mentioned transparent electrode pattern and in the above-mentioned non-pattern area.

The lamination step is not particularly limited, and may include, for example, a transfer step, a coating step, a step of bonding through an adhesive, and the like.
In the method for producing a composite with a transparent electrode of the present invention, the laminating step is to transfer an optical adjustment member and a transparent protective layer from a transfer film of the present invention described later on a transparent electrode pattern disposed on a substrate. It is preferably a step. With this configuration, the optical adjustment member of the composite with a transparent electrode and the above-described transparent protective layer can be collectively transferred, and without using a high refractive index transparent film on the substrate side of the transparent electrode pattern, It is possible to easily produce a composite with a transparent electrode excellent in concealing properties of a transparent electrode pattern, reducing unevenness caused by an optical adjustment member, and excellent in pencil hardness with high productivity.

The method for producing a composite with a transparent electrode of the present invention is characterized in that the low-refractive index layer and the high-refractive index layer are curable transparent resin layers containing a polymerizable compound, and the curability before being laminated on the transparent electrode pattern. It is preferable that the transparent resin layer is uncured.
The method for producing the composite with a transparent electrode preferably includes a step of simultaneously curing the transparent protective layer and the optical adjustment member, and more preferably includes a step of simultaneously pattern curing. After laminating the transparent protective layer, it is preferable to laminate the optical adjustment member without curing the transparent protective layer. The transparent protective layer and the optical adjustment member thus obtained can be cured at the same time. Thereby, after laminating the transparent protective layer and the optical adjustment member on the transparent electrode pattern, it can be developed into a desired pattern by photolithography.
The method for producing a composite with a transparent electrode includes, after a step of simultaneously curing the transparent protective layer and the optical adjustment member, an uncured portion of the transparent protective layer and the optical adjustment member (in the case of light curing, only an unexposed portion, or It is more preferable to include a step of developing and removing the exposed portion only).

  The method of forming the above-mentioned transparent protective layer and the above-mentioned optical adjustment member includes a protective film removing step of removing the above-mentioned protective film from the transfer film of the present invention, and a transfer film of the present invention from which the above-mentioned protective film has been removed. A transfer step of transferring the above-mentioned transparent protective layer and the above-mentioned optical adjustment member onto a transparent electrode pattern disposed on a substrate, and the above-mentioned transparent protective layer and the above-mentioned optical adjustment member transferred onto the transparent electrode pattern. A method including an exposing step of exposing, and a developing step of developing the exposed transparent protective layer and the above-described optical adjustment member are exemplified.

(Transfer process)
The case where the stacking step is a transfer step will be described. The transfer step is preferably a step of transferring the optical adjustment member and the transparent protective layer from the transfer film of the present invention onto the transparent electrode pattern disposed on the substrate. FIG. 16 is a schematic cross-sectional view showing an example of a transparent electrode pattern disposed on a substrate, which is used in the method for producing a composite with a transparent electrode of the present invention. In the transparent electrode pattern arranged on the substrate shown in FIG. 16, the transparent electrode pattern 4 is arranged on the substrate 1 via the transparent film 11. For example, after removing the protective film 29 from the transfer film 30 shown in FIG. 12, the low refractive index layer 12A and the high refractive index layer are formed on the transparent electrode pattern 4 arranged on the base material 1 shown in FIG. By transferring the optical adjustment member 12 made of 12B and the transparent protective layer 7, the composite with a transparent electrode of the present invention shown in FIG. 17 is obtained.
At this time, a method including a step of removing the temporary support after laminating the above-mentioned transparent protective layer and the above-mentioned optical adjustment member of the transfer film of the present invention on the transparent electrode pattern is preferable.
The transfer (lamination) of the above-mentioned transparent protective layer and the above-mentioned optical adjustment member to the surface of the transparent electrode pattern is performed by overlapping the above-mentioned transparent protective layer and the above-mentioned optical adjustment member on the surface of the transparent electrode pattern, and pressing and heating. Done in For lamination, a known laminator such as a laminator, a vacuum laminator, and an auto-cut laminator that can further improve the productivity can be used.

(Exposure step, development step, and other steps)
As examples of the above-described exposure step, development step, and other steps, the methods described in paragraphs 0035 to 0051 of JP-A-2006-23696 can be suitably used in the present invention.

The above-mentioned exposure step is preferably a step of exposing the above-mentioned transparent protective layer transferred onto the transparent electrode pattern and the above-mentioned optical adjustment member.
Specifically, a predetermined mask is arranged above the above-mentioned transparent protective layer formed on the above-mentioned transparent electrode pattern, the above-mentioned optical adjustment member, and the temporary support, and then a light source above the mask (mask, temporary) A method of exposing the above-mentioned transparent protective layer and the above-mentioned optical adjustment member (via a support) is included.
Here, a light source for the above-mentioned exposure is appropriately selected and used as long as it can emit light (for example, 365 nm, 405 nm, etc.) in a wavelength range capable of curing the above-mentioned transparent protective layer and the above-mentioned optical adjustment member. be able to. Specifically, an ultra-high pressure mercury lamp, a high pressure mercury lamp, a metal halide lamp and the like can be mentioned. The exposure amount is usually about 5 to 200 mJ / cm ² , preferably about 10 to 100 mJ / cm ² .

The above-mentioned developing step is preferably a step of developing the exposed transparent protective layer and the optical adjustment member.
In the present invention, the above-described development step is a development step in a narrow sense of pattern-developing the above-mentioned pattern-exposed transparent protective layer and the above-mentioned optical adjustment member with a developer.
The above-mentioned development can be performed using a developer. The developing solution is not particularly limited, and a known developing solution such as the developing solution described in JP-A-5-72724 can be used. The developing solution is preferably a developing solution in which the photocurable resin layer has a dissolving-type developing behavior. For example, pKa (The negative logarithm of the acid dissociation constant; Ka is a compound of acid dissociation constant) = 0 to 13 is used. A developer containing a concentration of 0.05 to 5 mol / L is preferable. On the other hand, the developer in the case where the above-mentioned transparent protective layer and the above-mentioned optical adjustment member itself do not form a pattern is preferably a developer having a type of developing behavior that does not dissolve the aforementioned non-alkali development type coloring composition layer. A developer containing a compound having a pKa of 7 to 13 at a concentration of 0.05 to 5 mol / L is preferable. A small amount of an organic solvent miscible with water may be added to the developer. Examples of water-miscible organic solvents include methanol, ethanol, 2-propanol, 1-propanol, butanol, diacetone alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-butyl ether, and benzyl alcohol. , Acetone, methyl ethyl ketone, cyclohexanone, ε-caprolactone, γ-butyrolactone, dimethylformamide, dimethylacetamide, hexamethylphosphoramide, ethyl lactate, methyl lactate, ε-caprolactam, N-methylpyrrolidone, and the like. The concentration of the organic solvent is preferably from 0.1% by mass to 30% by mass.
Further, a known surfactant can be further added to the developer. The concentration of the surfactant is preferably from 0.01% by mass to 10% by mass.

  The above-mentioned development method may be any of paddle development, shower development, shower & spin development, dip development, and the like. Here, the above-mentioned shower development will be described. Uncured portions can be removed by spraying a developing solution onto the above-mentioned transparent protective layer and the above-mentioned optical adjustment member after exposure with a shower. If a thermoplastic resin layer or an intermediate layer is provided, an alkaline liquid having low solubility of the transparent protective layer and the optical adjustment member is sprayed by a shower or the like before development, so that the thermoplastic resin layer, the intermediate layer, etc. It is preferable to remove them. After the development, it is preferable to remove a development residue while spraying a detergent or the like with a shower and rubbing with a brush or the like. The temperature of the developer is preferably from 20C to 40C, and the pH (power of Hydrogen) of the developer is preferably from 8 to 13.

  The above-described method for manufacturing the capacitance-type input device may include other steps such as a post-exposure step and a post-bake step. When the above-mentioned transparent protective layer and the above-mentioned optical adjustment member are thermosetting, it is preferable to perform a post-baking step.

  Note that the patterning exposure and the entire surface exposure may be performed after the temporary support is peeled off, or may be performed before the temporary support is peeled off, and then the temporary support may be peeled off. Exposure through a mask or digital exposure using a laser or the like may be used.

[Transfer film]
The transfer film of the present invention is a temporary support, a transparent protective layer, a transfer film having an optical adjustment member and a protective film in this order,
The optical adjustment member has at least one layer each of a low-refractive-index layer disposed odd-numbered from the protective film side and a high-refractive-index layer disposed evenly from the protective film side,
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The thickness of each of the low refractive index layer and the high refractive index layer is 5 to 80 nm.
The transparent electrode pattern (preferably including a metal oxide such as Indium Tin Oxide; ITO) generally has a refractive index higher than 2.10. Since the transfer film of the present invention has an optical adjustment member including a high refractive index layer having a refractive index of 2.10 or less and a transparent protective layer, the refractive index difference between the transparent electrode pattern and the optical adjustment member, and the optical adjustment member A composite with a transparent electrode having a small difference in refractive index between the transparent electrode and the transparent protective layer can be obtained. By forming the optical adjustment member and the transparent protective layer on the viewing side with respect to the transparent electrode pattern, light reflection is reduced, the transparent electrode pattern becomes difficult to see, and the transparent electrode pattern concealment can be improved.
In the transfer film of the present invention, the low refractive index layer and the high refractive index layer are preferably curable transparent resin layers containing a polymerizable compound, and the curable transparent resin layer is preferably uncured. In this case, even if the transfer film of the present invention is laminated with the optical adjustment member while the transparent protective layer has curability, the layer separation becomes good, and the opacity of the transparent electrode pattern by the above mechanism is improved. Can be improved. Further, in this case, after transferring the transparent protective layer and the optical adjustment member from the transfer film onto the transparent electrode pattern, the transparent protective layer and the optical adjustment member can be developed into a desired pattern by photolithography.
When the layer separation of the transparent protective layer and the optical adjustment member is good, the effect of adjusting the refractive index obtained by the above-described mechanism is easily obtained, and the concealment of the transparent electrode pattern tends to be improved. . Photolithography is preferably performed at least on a transparent protective layer that is a layer closer to the outside than the optical adjustment member after transfer. The optical adjustment member that becomes a layer closer to the inside than the transparent protective layer after the transfer need not have photolithography. In the present invention, the transparent protective layer preferably has curability in the state of a transfer film, and the transparent protective layer which is closer to the outside than the optical adjustment member after transfer preferably has photolithographic properties.
Hereinafter, preferred embodiments of the transfer film of the present invention will be described.

<Layer structure of transfer film>
The transfer film of the present invention has a temporary support, a transparent protective layer, an optical adjustment member, and a protective film in this order. The temporary support and the transparent protective layer may be disposed directly in contact with each other, or may be disposed via another layer. Examples of other layers include a thermoplastic resin layer and an intermediate layer described below. It is preferable that the temporary support and the transparent protective layer are disposed in direct contact with each other.
FIG. 12 shows an example of a preferred layer configuration of the transfer film of the present invention. FIG. 12 is a schematic view of the transfer film 30 of the present invention in which the temporary support 26, the transparent protective layer 7, the optical adjustment member 12, and the protective film 29 are laminated adjacent to each other in this order. In FIG. 12, the low refractive index layer 12 </ b> A in which the optical adjustment member 12 is arranged in an odd number from the protective film 29 side (the side opposite to the transparent protective layer 7), and the protective film 29 side (the side opposite to the transparent protective layer 7). ) And the even-numbered high refractive index layers 12B.

  Although the transfer film of the present invention is preferably a negative material, the transfer film of the present invention may be a positive material. When the transfer film of the present invention is a positive-type material, for example, a material described in JP-A-2005-221726 is used for the transparent protective layer and the optical adjustment member, but is not limited thereto.

<Temporary support>
The temporary support used for the transfer film of the present invention is not particularly limited, and examples thereof include glass, Si wafer, paper, nonwoven fabric, and film. Among them, the temporary support is preferably a film, and more preferably a resin film.
As the film used as the temporary support, a material which is flexible and does not significantly deform, shrink, or elongate under pressure or under pressure and heat can be used. Examples of the temporary support satisfying this property include a polyethylene terephthalate film, a cellulose triacetate film, a polystyrene film, and a polycarbonate film. Among them, a biaxially stretched polyethylene terephthalate film is particularly preferable.

The thickness of the temporary support is not particularly limited, and is generally in the range of 5 to 200 μm, and is particularly preferably in the range of 10 to 150 μm from the viewpoint of ease of handling and versatility, and is preferably 10 to 150 μm from the viewpoint of weight reduction. The range of ２０20 μm is more preferable.
The temporary support may be transparent or may contain dyed silicon, alumina sol, chromium salt, zirconium salt, or the like.
Further, the temporary support can be provided with conductivity by a method described in JP-A-2005-221726 or the like.

<Transparent protective layer>
The preferred range of the transparent protective layer of the transfer film is the same as the preferred range of the transparent protective layer of the composite with a transparent electrode.
When the transparent protective layer is curable, the transfer film of the present invention can impart photolithography to the transparent protective layer after transfer. In the transfer film of the present invention, the transparent protective layer preferably contains a resin soluble in an organic solvent. On the other hand, the low refractive index layer and the high refractive index layer included in the optical adjustment member are preferably formed from an aqueous resin composition, but the formed low refractive index layer and high refractive index layer are formed of a water-soluble resin. It is preferable that the formed low refractive index layer and high refractive index layer include a resin soluble in a basic aqueous solution (for example, ammonia water). When producing the transfer film of the present invention, the organic solvent-based resin composition used to form the transparent protective layer is applied, dried, and then subjected to low-refractive-index layers included in the above-described optical adjustment member without exposure. It is preferable to apply a water-based resin composition used for forming a high refractive index layer to impart curability to the transparent protective layer in a state of being used as a dry resist film.

<Optical adjustment member>
The transfer film of the present invention has an optical adjustment member, and the optical adjustment member includes an odd-numbered low refractive index layer arranged from the protective film side and a high refractive index layer arranged evenly from the protective film side. Each has at least one layer,
The difference in the refractive index between the low refractive index layer and the high refractive index layer directly adjacent thereto is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The thickness of each of the low refractive index layer and the high refractive index layer is 5 to 80 nm.
The preferred range of the optical adjustment member of the transfer film is the same as the preferred range of the optical adjustment member of the composite with a transparent electrode.

<Protective film>
The transfer film of the present invention preferably has a protective film, and preferably has a protective film (also referred to as “protective release layer”) on the surface of the optical adjustment member.

  As the above-mentioned protective film, the protective films described in paragraphs 0083 to 0087 and 0093 of JP-A-2006-259138 can be appropriately used.

<Thermoplastic resin layer>
In the transfer film, a thermoplastic resin layer may be provided between the temporary support and the transparent protective layer.
The above-mentioned thermoplastic resin layer is preferably alkali-soluble. The thermoplastic resin layer plays a role as a cushion material so as to be able to absorb irregularities (including irregularities caused by an already formed image or the like) on the surface of the base, and has a role of a cushion material. It is preferable to have a property that can be deformed according to.

  The thermoplastic resin layer preferably contains an organic polymer substance described in JP-A-5-72724 as a component, and is preferably formed by a Vicat method (specifically, based on American Material Testing Method ASTM D1235). Polymer softening point measurement method] is particularly preferred in which the softening point includes at least one selected from organic polymer substances having a softening point of about 80 ° C. or lower.

  Specifically, polyethylene, polyolefins such as polypropylene, ethylene copolymers with ethylene and vinyl acetate or saponified products thereof, copolymers of ethylene with acrylic acid esters or saponified products thereof, polyvinyl chloride or vinyl chloride and Vinyl acetate copolymer with vinyl acetate or saponified product thereof, polyvinylidene chloride, vinylidene chloride copolymer, polystyrene, styrene copolymer with styrene and (meth) acrylic acid ester or saponified product thereof, polyvinyl toluene , Vinyl toluene copolymer of vinyl toluene and (meth) acrylate or saponified product thereof, poly (meth) acrylate, (meth) acrylate of butyl (meth) acrylate and vinyl acetate, etc. Polymer, vinyl acetate copolymer nylon, copolymer nylon Emissions, N- alkoxymethyl nylon, and organic polymers such as polyamide resins such as N- dimethylamino nylon.

  The thickness of the thermoplastic resin layer is preferably 3 to 30 μm. The thickness of the above-mentioned thermoplastic resin layer is more preferably 4 to 25 μm, and particularly preferably 5 to 20 μm.

  The thermoplastic resin layer can be formed by applying a preparation liquid containing a thermoplastic organic polymer or the like, and the preparation liquid used for the coating or the like can be prepared using a solvent. The solvent is not particularly limited as long as it can dissolve the polymer component constituting the thermoplastic resin layer, and examples thereof include methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, n-propanol, 2-propanol and the like.

<Intermediate layer>
In the transfer film, an intermediate layer may be provided between the above-mentioned thermoplastic resin layer and the above-mentioned transparent protective layer. As the intermediate layer, a layer described as a "separation layer" in JP-A-5-72724 is preferable.

<Method for manufacturing transfer film>
The method for manufacturing the transfer film is not particularly limited, and the transfer film can be manufactured by a known method.
The transfer film includes a step of forming a transparent protective layer on the temporary support, a step of forming an optical adjustment member on the transparent protective layer, and a step of forming a protective film on the optical adjustment member. It is preferable to be manufactured by a manufacturing method having
In the method for producing a transfer film, it is preferable to suppress the interlayer mixing between the transparent protective layer and the optical adjustment member. For this purpose, the composition for forming a transparent protective layer (for example, a coating solution) is an organic solvent-based resin composition, and a composition for forming a low refractive index layer and a composition for forming a high refractive index layer (for example, a coating solution) of an optical adjustment member. ) Is preferably an aqueous resin composition. In this case, even if the composition for forming a low refractive index layer and the composition for forming a high refractive index layer are applied thereon without curing the composition for forming a transparent protective layer, the transparent protective layer does not dissolve. Difficult to do.
The step of forming a transparent protective layer is a step of applying an organic solvent-based resin composition containing a resin soluble in an organic solvent on the temporary support, and the low refractive index layer and the high refractive index layer of the optical adjustment member. When the step of forming is a step of applying the aqueous resin composition, the uniformity of the thickness of the low refractive index layer and the high refractive index layer of the optical adjustment member is good, and color unevenness is significantly reduced, which is preferable. . The aqueous resin composition preferably contains "a resin soluble in water, or a resin not soluble in water but soluble in aqueous ammonia", and "a resin not soluble in water but soluble in aqueous ammonia." It is more preferable to include "a suitable resin". Specifically, when a water-based resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group is applied on a transparent protective layer obtained by an organic solvent-based resin composition, the transparent protective layer Even if the low refractive index layer and the high refractive index layer of the optical adjustment member are formed without curing, the interlayer mixing becomes difficult to occur, and the uniformity of the thickness of the low refractive index layer and the high refractive index layer of the optical adjustment member is good. Becomes

  At this time, photolithography can be imparted by including the resin of the transparent protective layer with a resin having photolithography. Examples of the resin having photolithography properties include a specific acrylic resin and the like, and an acrylic resin that is an alkali-soluble resin is preferable, and acrylic resins described in JP-A-2008-146018, [0028] to [0072]. Is more preferred.

  Further, the resin of the low refractive index layer and the resin of the high refractive index layer of the optical adjustment member contains an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, thereby improving the wet heat durability of the obtained layer. be able to. Specifically, when drying a coating film obtained by using an aqueous resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group, an ammonium salt or an acid of a monomer having an acid group is used. Ammonia having a lower boiling point than water tends to volatilize in the drying step from the ammonium salt of the resin having a group. Therefore, an acid group can be generated (regenerated) to be present in the low refractive index layer and the high refractive index layer as a monomer having an acid group or a resin having an acid group. Therefore, when aged under high temperature and high humidity and allowed to absorb moisture, the monomer having an acid group or the resin having an acid group that constitutes the low-refractive index layer and the high-refractive index layer is no longer dissolved in water, and is thus transferred. The problem of wet heat durability when the film absorbs moisture can also be suppressed.

  Furthermore, since the composition for forming a transparent protective layer (for example, a coating solution) contains a surfactant containing a fluorine atom (also referred to as a fluorine-based surfactant), the composition of the optical adjustment member can be hardened without curing the transparent protective layer. Even when the low refractive index layer and the high refractive index layer are formed, no interlayer mixing occurs, and the uniformity of the thickness of the low refractive index layer and the high refractive index layer of the optical adjustment member is improved. Further, by adjusting the content of the surfactant in the composition for forming a transparent protective layer so that the content based on the solid content of the surfactant in the transparent protective layer is 0.01 to 0.50 mass%, When a composite with a transparent electrode described later is manufactured, the adhesion between the optical adjustment member and the transparent electrode pattern is improved. The preferred range of the content of the surfactant with respect to the solid content of the composition for forming the transparent protective layer is the preferred range of the amount in which the transparent protective layer contains a surfactant containing a fluorine atom with respect to the solid content of the transparent protective layer. The same is true.

  In particular, the step of forming the transparent protective layer described above is a step of applying an organic solvent-based resin composition containing an acrylic resin and a surfactant containing a fluorine atom on the temporary support, and the optical adjustment described above. It is preferable that the step of forming the member is a step of applying an aqueous resin composition containing an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group. This embodiment is preferable because intermixing between the transparent protective layer and the optical adjustment member can be suppressed, the uniformity of the thickness of the optical adjustment member is improved, and color unevenness is significantly reduced. According to this aspect, the adhesion between the optical adjustment member and the transparent electrode pattern is further improved, and the transparent resin layer formed using the aqueous resin composition when aged at high temperature and high humidity (here, This is preferable because the problem caused by moisture absorption of the optical adjustment member can be suppressed.

(Step of forming transparent protective layer on temporary support)
The step of forming the transparent protective layer on the temporary support is preferably a step of applying a resin composition for forming a transparent protective layer on the temporary support.
The resin composition for forming the transparent protective layer preferably has a solid content of 15 to 30% by mass, more preferably 20 to 24% by mass, and particularly preferably 21 to 23% by mass.
It is more preferable that the step of forming the transparent protective layer on the temporary support is a step of applying the organic solvent-based resin composition on the above-mentioned temporary support.

The organic solvent-based resin composition refers to a resin composition that can be dissolved in an organic solvent.
As the organic solvent, a general organic solvent can be used. Examples of the organic solvent include methyl ethyl ketone, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, methyl isobutyl ketone, ethyl lactate, methyl lactate, caprolactam and the like.

  It is preferable that the resin composition used for forming the transparent protective layer contains a binder polymer, a photopolymerizable compound, and a photopolymerization initiator.

-Binder polymer-
As the binder polymer contained in the resin composition used for forming the above-mentioned transparent protective layer, any polymer component can be used without particular limitation. As the binder polymer, those having high surface hardness and high heat resistance are preferable, and alkali-soluble resins are more preferable, from the viewpoint of use as a transparent protective layer of a capacitance-type input device, particularly as a protective film for a transparent electrode. Among the alkali-soluble resins, known photosensitive siloxane resin materials and acrylic resin materials are preferably used. The binder polymer contained in the resin composition used for forming the transparent protective layer is preferably an acrylic resin. Both the binder polymer contained in the resin composition used for forming the transparent protective layer and the resin or binder polymer having an acid group contained in the resin composition used for forming the optical adjustment member described below contain an acrylic resin. Is more preferable from the viewpoint of enhancing the interlayer adhesion before and after the transfer of the transparent protective layer and the optical adjustment member. The preferred range of the binder polymer of the transparent protective layer will be specifically described.

  The resin (also referred to as a “binder” or “polymer”) used in the organic solvent-based resin composition used for forming the above-described transparent protective layer and having solubility in an organic solvent is within the scope of the present invention. There is no particular limitation as long as it is not adversely affected, and it can be appropriately selected from known ones, and an alkali-soluble resin is preferred. As the above-mentioned alkali-soluble resin, polymers described in paragraph 0025 of JP-A-2011-95716 and paragraphs 0033 to 0052 of JP-A-2010-237589 can be used.

  Further, the resin composition used for forming the transparent protective layer may include a polymer latex. The polymer latex referred to here is one in which fine particles of a water-insoluble polymer are dispersed in water. The polymer latex is described, for example, in Soichi Muroi, Chemistry of Polymer Latex (published by the Society of Polymer Publishing (Showa 48)).

Examples of the polymer particles that can be used include acrylic, vinyl acetate, rubber (eg, styrene-butadiene, chloroprene), olefin, polyester, polyurethane, and polystyrene polymers, and polymers composed of copolymers thereof. Particles are preferred.
It is preferable to increase the bonding force between the polymer chains constituting the polymer particles. Means for increasing the bonding force between polymer chains include a means utilizing an interaction caused by a hydrogen bond and a means for generating a covalent bond.
As means for utilizing the interaction caused by hydrogen bonding, it is preferable to introduce a monomer having a polar group in the polymer chain by copolymerization or graft polymerization. The polar group of the binder polymer includes a carboxyl group (contained in acrylic acid, methacrylic acid, itaconic acid, fumaric acid, maleic acid, crotonic acid, partially esterified maleic acid, etc.), primary, secondary and tertiary amino groups , An ammonium base, a sulfonic group (such as a styrene sulfonic group), and a carboxyl group and a sulfonic group are particularly preferable. A preferable range of the copolymerization ratio of the monomer having a polar group is 5 to 35% by mass, more preferably 5 to 20% by mass, and still more preferably 15 to 20% by mass with respect to 100% by mass of the polymer. It is.
On the other hand, as a means for forming a covalent bond, for at least one of a hydroxyl group, a carboxyl group, a primary or secondary amino group, an acetoacetyl group and a sulfonic acid group, an epoxy compound, a blocked isocyanate, an isocyanate, Examples include a method of reacting at least one of a vinyl sulfone compound, an aldehyde compound, a methylol compound, and a carboxylic anhydride.
Among polymers utilizing these reactions, a polyurethane derivative obtained by the reaction of a polyol and a polyisocyanate compound is preferable, and a polyvalent amine is more preferably used in combination as a chain extender, and further, the polar group is introduced into a polymer chain. The ionomer type is particularly preferable.
The weight average molecular weight of the polymer is preferably 10,000 or more, more preferably 20,000 to 100,000. Polymers suitable for the present invention include ethylene ionomers and polyurethane ionomers, which are copolymers of ethylene and methacrylic acid.

The polymer latex that can be used in the present invention may be one obtained by emulsion polymerization or one obtained by emulsification. The method for preparing these polymer latexes is described, for example, in "Emulsion Latex Handbook" (edited by the Emulsion Latex Handbook Editing Committee, published by Taisei Co., Ltd. (1975)).
Examples of the polymer latex that can be used in the present invention include an aqueous dispersion of polyethylene ionomer (trade name: Chemipearl S120, manufactured by Mitsui Chemicals, Inc .; solid content: 27% by mass) (tradename: Chemipearl S100, Mitsui Chemicals, Inc.) (Trade name: Chemipearl S111, manufactured by Mitsui Chemicals, Inc .; solid content 27% by mass) (trade name: Chemipearl S200, manufactured by Mitsui Chemicals, Inc., solid content 27% by mass) (trade name: Chemipearl S300, manufactured by Mitsui Chemicals, Inc., solid content 35% by mass) (trade name: Chemipearl S650, manufactured by Mitsui Chemicals, Inc .; solids content 27% by mass) (trade name: Chemipearl S75N, manufactured by Mitsui Chemicals, Inc., solid content 24) Mass%) or an aqueous dispersion of a polyether-based polyurethane (trade name: Hydran WLS-201 DIC Corporation; solid). 35% by mass, Tg-50 ° C, Tg is an abbreviation of Glass Transition Temperature (trade name: Hydran WLS-202 manufactured by DIC Corporation. Solid content 35% by mass, Tg-50 ° C) (trade name: Hydran WLS- 221 DIC Corporation, solid content 35% by mass, Tg-30 ° C) (trade name: Hydran WLS-210 DIC Corporation, solid content 35% by mass, Tg-15 ° C) (trade name: Hydran WLS- 213 DIC Corporation, solid content 35% by mass, Tg-15 ° C) (trade name: Hydran WLI-602 DIC Corporation, solid content 39.5% by mass, Tg-50 ° C) (trade name: Hydran WLI-611 DIC Co., Ltd. Solid content 39.5% by mass, Tg-15 ° C), alkyl acrylate copolymer ammonium (trade name: Julimer AT) 210 (manufactured by Toagosei Co., Ltd.) (trade name: Julimer ET-410 manufactured by Toagosei Co., Ltd.) (commercial name: Julimer AT-510 manufactured by Toagosei Co., Ltd.), polyacrylic acid (tradename: Julimer AC-10L) Toagosei Co., Ltd.) is neutralized with ammonia and emulsified.

-Photopolymerizable compound-
As the photopolymerizable compound used in the water-based resin composition or the organic solvent-based resin composition, the photopolymerizable compounds described in paragraphs 0023 to 0024 of Japanese Patent No. 4098550 can be used. Among them, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tetraacrylate of pentaerythritol ethylene oxide adduct can be preferably used. These photopolymerizable compounds may be used alone or in combination of two or more. When a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is used, the mass ratio of pentaerythritol triacrylate to the entire mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is preferably 0 to 80%, and more preferably 10 to 80%. More preferably, it is 60%.
Examples of the photopolymerizable compound used in the organic solvent-based resin composition include polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, trimethylolethanetri (meth) acrylate, trimethylolpropanetri (meth) acrylate, Trimethylolpropane di (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) Acrylate, hexanediol di (meth) acrylate, trimethylolpropane tri (acryloyloxypropyl) ether, tri (acryloyloxyethyl) (Meth) acrylated after adding ethylene oxide or propylene oxide to isocyanurate, tri (acryloyloxyethyl) cyanurate, glycerin tri (meth) acrylate, polymethyl alcohol such as trimethylolpropane, glycerin, bisphenol, etc. Urethane acrylates described in JP-B-48-41708, JP-B-50-6034, JP-A-51-37193 and the like; JP-A-48-64183, JP-B-49-43191; Polyester acrylates described in JP-B-52-30490 and the like; polyfunctional acrylates and methacrylates such as epoxy acrylates which are reaction products of epoxy resin and (meth) acrylic acid. Among them, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate pentaerythritol tetraacrylate mixture (NK ester A-TMMT New Nakamura Chemical Industry Co., Ltd.) and tetraacrylate of pentaerythritol ethylene oxide adduct (Kayarad RP-1040 manufactured by Nippon Kayaku Co., Ltd.) can be preferably used. These may be used alone or in combination of two or more.

-Photopolymerization initiator-
When the resin composition used to form the transparent protective layer contains the photopolymerizable compound and the photopolymerization initiator, the pattern of the transparent protective layer can be easily formed.
As the photopolymerization initiator used in the organic solvent-based resin composition, the photopolymerization initiators described in paragraphs 0031 to 0042 of JP-A-2011-95716 can be used. For example, in addition to 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1- [9- Ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), 2- (dimethylamino) -2 -[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (trade name: Irgacure 379EG, manufactured by BASF), 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (trade name: Irgacure 907, manufactured by BASF), 2-hydroxy-1- {4- [4- (2-hydro Xy-2-methyl-propionyl) -benzyl] phenyl} -2-methyl-propan-1-one (trade name: Irgacure 127, manufactured by BASF), 2-benzyl-2-dimethylamino-1- (4-morpholino Phenyl) -butanone-1 (trade name: Irgacure 369, manufactured by BASF), 2-hydroxy-2-methyl-1-phenyl-propan-1-one (trade name: Irgacure 1173, manufactured by BASF), 1-hydroxy-cyclohexyl -Phenyl-ketone (trade name: Irgacure 184, manufactured by BASF), 2,2-dimethoxy-1,2-diphenylethan-1-one (trade name: Irgacure 651, manufactured by BASF), oxime ester-based photopolymerization initiator (Product name: Lunar 6, manufactured by DKSH Japan KK) It can be used properly.
In the resin composition used for forming the transparent protective layer, the photopolymerization initiator is contained in an amount of 1% by mass or more based on the solid content of the resin composition used for forming the transparent protective layer. , And more preferably 2% by mass or more. In the resin composition used for forming the transparent protective layer, the photopolymerization initiator is contained in an amount of 10% by mass or less based on the solid content of the resin composition used for forming the transparent protective layer. And more preferably 5% by mass or less from the viewpoint of improving the patterning property of the composite with a transparent electrode of the present invention.

-Metal oxide particles-
The resin composition used to form the above-mentioned transparent protective layer may or may not contain particles (preferably metal oxide particles) for the purpose of adjusting the refractive index and light transmittance. . In order to control the refractive index of the above-mentioned transparent protective layer in the above-mentioned range, metal oxide particles are included in an arbitrary ratio depending on the type of the polymer or the polymerizable compound (preferably, the photopolymerizable compound) used. Can be. In the resin composition used for forming the transparent protective layer, the metal oxide particles are contained in an amount of 0 to 35% by mass based on the solid content of the resin composition used for forming the transparent protective layer. It is more preferably contained in an amount of 0 to 10% by mass, and particularly preferably not contained.

(Step of forming optical adjustment member)
The step of forming the optical adjustment member on the transparent protective layer is performed by forming a resin composition for forming an optical adjustment member (a resin composition for forming a low refractive index layer or a resin composition for forming a high refractive index layer) on the transparent protective layer. (Composition) is preferably applied.
The resin composition for forming an optical adjustment member preferably has a solid content concentration of 1.0 to 5.0% by mass, more preferably 1.2 to 3.0% by mass, and more preferably 1.5 to 3.0% by mass. Particularly preferred is 2.0% by mass.
More preferably, the step of forming the optical adjustment member directly on the transparent protective layer is a step of applying an aqueous resin composition for forming the optical adjustment member. The step of forming the optical adjustment member directly on the transparent protective layer is a step of applying an aqueous resin composition for forming an optical adjustment member including an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group. Is particularly preferred.

The aqueous resin composition refers to a resin composition that can be dissolved in an aqueous solvent.
The resin composition for forming an optical adjustment member preferably has a water content of 15 to 85 parts by mass, more preferably 20 to 80 parts by mass, based on 100 parts by mass of the total solvent, and 25 to 80 parts by mass. It is particularly preferred that the amount be from 75 to 75 parts by mass.
As the aqueous solvent, water or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms and water is preferable. The solvent of the aqueous resin composition used for forming the optical adjustment member preferably contains water and an alcohol having 1 to 3 carbon atoms, and the content of water / the alcohol having 1 to 3 carbon atoms is 15/85 by mass ratio. More preferably, it is water of 85 to 15 or a mixed solvent. The content ratio of water / alcohol having 1 to 3 carbon atoms is particularly preferably in a range of 20/80 to 80/20 by mass ratio, and more preferably in a range of 25/75 to 75/25.
The pH at 25 ° C. of the aqueous resin composition is preferably from 7.0 to 12.0, more preferably from 7.0 to 10.0, and preferably from 7.0 to 8.5. Particularly preferred. For example, the pH of the aqueous resin composition can be adjusted to the above preferred range by using an excess amount of ammonia with respect to the acid group and adding a monomer having an acid group or a resin having an acid group.

Further, the resin composition used for forming the optical adjustment member is preferably at least one of thermosetting and photocuring. When the transparent protective layer and the optical adjustment member are a curable transparent resin layer, even if the optical adjustment member is laminated without curing after laminating the transparent protective layer, the layer separation becomes good and the opacity of the transparent electrode pattern is improved. Can be improved. In the case where the transparent protective layer is a curable transparent resin layer, the composite with a transparent electrode described below simultaneously forms an overcoat layer and a refractive index adjusting layer (that is, a transparent protective layer and an optical adjusting member) from the obtained transfer film. After the transfer on the transparent electrode pattern, the transparent protective layer, which is a layer closer to the outside than the optical adjustment member at least after transfer by photolithography, can be developed into a desired pattern. Further, an embodiment in which the optical adjustment member has curability is more preferable. In this embodiment, after the transparent protective layer and the optical adjustment member are simultaneously transferred onto the transparent electrode pattern, they can be simultaneously developed into a desired pattern by photolithography.
It is preferable that the resin composition used for forming the optical adjustment member includes a binder polymer, a light or heat polymerizable compound, and a light or heat polymerization initiator.

More preferably, the resin composition used for forming the optical adjustment member has an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group. The aqueous resin composition preferably contains an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group.
The ammonium salt of a monomer having an acid group or the ammonium salt of a resin having an acid group is not particularly limited. It is preferable that the above-mentioned ammonium salt of the monomer having an acid group or the ammonium salt of the resin having an acid group of the optical adjustment member is an acrylic monomer having an acid group or an ammonium salt of an acrylic resin. Only the ammonium salt of the resin having an acid group may be the binder polymer, and another binder polymer may be used in addition to the ammonium salt of the resin having the acid group. The ammonium salt of the monomer having an acid group may be a photo- or thermo-polymerizable compound, and a photo- or thermo-polymerizable compound may be used in addition to the ammonium salt of the monomer having an acid group.
A method for producing a transfer film includes a step of dissolving a monomer having an acid group or a resin having an acid group in an aqueous ammonia solution to prepare an aqueous resin composition containing a monomer or resin in which at least a part of the above-described acid group is ammonium chloride. It is preferable to include
The concentration of the aqueous ammonia solution that can be used in the method for producing a transfer film is not particularly limited, but an aqueous ammonia solution having an ammonia concentration of 0.1 to 25% by mass is preferable, and an aqueous ammonia solution of 0.5 to 10% by mass is more preferable. A 1-5 mass% aqueous ammonia solution is particularly preferred.
The monomer having an acid group or the resin having an acid group is preferably a resin having an acid group.

-Binder polymer-
The resin composition used for forming the optical adjustment member preferably contains a binder polymer.
Examples of the binder polymer include a resin having an acid group and another binder polymer having no acid group.

--- Resin having acid group-
The resin having an acid group is more preferably a resin having a monovalent acid group (such as a carboxyl group).
The resin used in the aqueous resin composition used for forming the optical adjustment member and having solubility in an aqueous solvent (preferably water or a mixed solvent of lower alcohol having 1 to 3 carbon atoms and water) is the present invention. There is no particular limitation as long as it does not contradict the purpose of the invention, and it can be appropriately selected from known ones.
The resin having an acid group used in the aqueous resin composition is preferably an alkali-soluble resin. The alkali-soluble resin is a linear organic high molecular polymer, and has at least one group that promotes alkali dissolution in a molecule (preferably, a molecule having an acrylic copolymer or a styrene copolymer as a main chain). (That is, an acid group: for example, a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc.) can be appropriately selected from alkali-soluble resins having the same. Of these, those more preferably soluble in an organic solvent and developable with a weak alkaline aqueous solution are used. As the acid group, a carboxyl group is preferable.

  For the production of the alkali-soluble resin, for example, a method using a known radical polymerization method can be applied. Polymerization conditions such as temperature, pressure, type and amount of radical initiator, type of solvent, and the like when producing an alkali-soluble resin by a radical polymerization method can be easily set by those skilled in the art and experimentally determine conditions. You can also.

  As the above-mentioned linear organic high molecular polymer, a polymer having a carboxylic acid in a side chain is preferable. For example, JP-A-59-44615, JP-B-54-34327, JP-B-58-12577, JP-B-54-25957, JP-A-59-53836, JP-A-59-71048, and JP-A-59-71048. No. 46-2121 and JP-B-56-40824, poly (meth) acrylic acid, methacrylic acid copolymer, acrylic acid copolymer, itaconic acid copolymer, crotonic acid copolymer Coalescing, maleic acid copolymers such as styrene / maleic acid, partially esterified maleic acid copolymers, etc .; acidic cellulose derivatives having a carboxylic acid in the side chain such as carboxyalkyl cellulose and carboxyalkyl starch; and polymers having a hydroxyl group. Those to which an acid anhydride is added are preferred. Further, a polymer having a reactive functional group such as a (meth) acryloyl group in a side chain is also preferable.

Among these, benzyl (meth) acrylate / (meth) acrylic acid copolymer and multi-component copolymer composed of benzyl (meth) acrylate / (meth) acrylic acid / other monomer are particularly preferable.
In addition, those obtained by copolymerizing 2-hydroxyethyl methacrylate are also useful. This polymer can be used by mixing in an arbitrary amount.

  Other than the above, 2-hydroxypropyl (meth) acrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxy-3-phenoxypropyl acrylate / polymethyl methacrylate described in JP-A-7-140654 Macromonomer / benzyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / methyl methacrylate / methacrylic acid copolymer, 2-hydroxyethyl methacrylate / polystyrene macromonomer / benzyl methacrylate / methacrylic acid copolymer, etc. Is mentioned.

  As a specific structural unit of the alkali-soluble resin, a copolymer of (meth) acrylic acid and another monomer copolymerizable therewith is particularly suitable.

Examples of other monomers copolymerizable with (meth) acrylic acid include alkyl (meth) acrylate, aryl (meth) acrylate, and vinyl compound. Here, the hydrogen atom of the alkyl group and the aryl group may be substituted with a substituent.
Specific examples of the alkyl (meth) acrylate and the aryl (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, and pentyl (meth) acrylate. A) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, phenyl (meth) acrylate, benzyl acrylate, tolyl acrylate, naphthyl acrylate, cyclohexyl acrylate, and the like.

Examples of the vinyl compound include styrene, α-methylstyrene, vinyltoluene, glycidyl methacrylate, acrylonitrile, vinyl acetate, N-vinylpyrrolidone, tetrahydrofurfuryl methacrylate, polystyrene macromonomer, polymethyl methacrylate macromonomer, and CH ₂ = CR ¹ R ² , CH ₂ ＣC (R ¹ ) (COOR ³ ) and the like can be mentioned. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ² represents an aromatic hydrocarbon ring having 6 to 10 carbon atoms, and R ³ represents an alkyl group or 1 to 8 carbon atoms. Represents an aralkyl group represented by Formulas 6 to 12.
One of these other copolymerizable monomers can be used alone, or two or more can be used in combination. Preferred other copolymerizable monomers are selected from CH ₂ ＣＲCR ¹ R ² , CH ₂ ＣC (R ¹ ) (COOR ³ ), phenyl (meth) acrylate, benzyl (meth) acrylate and styrene. It is at least one kind, and particularly preferably CH ₂ ＣＲCR ¹ R ² and / or CH ₂ ＣC (R ¹ ) (COOR ³ ).

  In addition, a linear polymer having a substituent capable of reacting with the reactive functional group is reacted with a (meth) acrylic compound having a reactive functional group, cinnamic acid, etc., to form an ethylenically unsaturated double bond. Is introduced into this linear polymer. Examples of the reactive functional group include a hydroxyl group, a carboxyl group, and an amino group. Examples of the substituent capable of reacting with the reactive functional group include an isocyanate group, an aldehyde group, and an epoxy group.

  Among these, the resin having an acid group is preferably an acrylic resin having an acid group. In this specification, the acrylic resin includes both methacrylic resin and acrylic resin, and the (meth) acrylic includes methacrylic and acrylic.

-Other binder polymers-
The other binder polymer having no acid group is not particularly limited, and the binder polymer used in the resin composition used for forming the transparent protective layer described above can be used.

-Polymerizable compound-
It is preferable that the resin composition used for forming the optical adjustment member contains a polymerizable compound such as a photopolymerizable compound or a thermopolymerizable compound, from the viewpoint of increasing the strength of the film by curing.
Examples of the polymerizable compound included in the resin composition used for forming the optical adjustment member include a monomer having an acid group and a polymerizable compound other than the monomer having an acid group.
The polymerizable compound of the resin composition used for forming the optical adjustment member preferably contains a photopolymerizable compound other than the monomer having an acid group, and includes a monomer other than the monomer having an acid group and the monomer having an acid group. It is more preferable to include another photopolymerizable compound.

-Monomer having acid group-
As the monomer having an acid group, acrylic monomers such as (meth) acrylic acid and derivatives thereof, and the following monomers can be preferably used.
For example, a 3 to 4 functional radical polymerizable monomer (having a carboxylic acid group introduced into the pentaerythritol tri and tetraacrylate skeleton (acid value = 80 to 120 mg KOH / g)), a 5 to 6 functional radical polymerizable monomer (di- Pentaerythritol penta and those in which a carboxylic acid group is introduced into a hexaacrylate skeleton (acid value = 25 to 70 mgKOH / g). Although a specific name is not described, a bifunctional alkali-soluble radically polymerizable monomer may be used as necessary.
In addition, monomers having an acid group described in [0025] to [0030] of JP-A-2004-239942 can also be preferably used, and the contents of this publication are incorporated herein.
Among them, acrylic monomers such as (meth) acrylic acid and derivatives thereof can be more preferably used. In this specification, the acrylic monomer includes both a methacrylic monomer and an acrylic monomer.

その他の光学調整部材の形成に用いられる樹脂組成物に用いられる光重合性化合物としては、メタノールなどの炭素原子数１乃至３の低級アルコールと水との混合溶媒にも溶解性を有することが、後述する金属酸化物粒子のアルコール分散液を水系樹脂組成物である光学調整部材の形成に用いられる樹脂組成物に併用する場合に好ましい。水もしくは炭素原子数１乃至３の低級アルコールと水との混合溶媒に対して溶解性を有する重合性化合物としては、水酸基を有するモノマー、分子内にエチレンオキサイドやポリプロピレンオキサイド、およびリン酸基を有するモノマーが使用できる。炭素原子数１乃至３の低級アルコールと水との混合溶媒にも溶解性を有する重合性化合物としては、カヤラッドＲＰ−１０４０（日本化薬（株）製）、アロニックスＴＯ−２３４９（東亞合成社製）、重合性モノマー Ａ−９３００（新中村化学工業（社）製）、Ａ−ＧＬＹ−２０Ｅ（新中村化学工業（社）製）などが好ましい。なお、重合性化合物が炭素原子数１乃至３の低級アルコールと水との混合溶媒にも溶解性を有するとは、アルコールと水の混合溶媒に０．１質量％以上溶解することを言う。
また、重合性化合物の含有量は、光学調整部材を形成用の樹脂組成物の固形分の全質量に対し、０〜２０質量％であることが好ましく、０〜１０質量％であることがより好ましく、０〜５質量％であることが更に好ましい。--- Other polymerizable compounds--
As the polymerizable compound other than the monomer having an acid group used in the resin composition used for forming the optical adjustment member, a photopolymerizable compound is preferable.
As the photopolymerizable compound, the photopolymerizable compounds described in paragraphs 0023 to 0024 of Japanese Patent No. 4098550 can be used. Among them, pentaerythritol tetraacrylate, pentaerythritol triacrylate, and tetraacrylate of pentaerythritol ethylene oxide adduct can be preferably used. These polymerizable compounds may be used alone or in combination of two or more. When a mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is used, the ratio of pentaerythritol triacrylate to the entire mixture of pentaerythritol tetraacrylate and pentaerythritol triacrylate is preferably from 0 to 80% by mass, and preferably from 10 to 80% by mass. It is more preferable that the content is ６０60% by mass.
As the photopolymerizable compound used in the resin composition used for forming the optical adjustment member, specifically, a mixture of a water-soluble polymerizable compound represented by the following structural formula 1 and pentaerythritol tetraacrylate (NK ester A -TMMT manufactured by Shin-Nakamura Chemical Co., Ltd., containing about 10% of triacrylate as an impurity), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3LM-N manufactured by Shin-Nakamura Chemical Co., Ltd., triacrylate 37) Mass%), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM-3L manufactured by Shin-Nakamura Chemical Co., Ltd., 55 mass% of triacrylate), a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A) -TMM3 new Nakamura Chemical Co., Ltd., triacrylate 57 mass%), pentaerythritol ethylene oxide adduct tetraacrylate (Kayarad RP-1040, manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (Toagosei Co., Ltd.), etc. Can be mentioned.
Among the photopolymerizable compounds used in the resin composition used to form the optical adjustment member, among these, from the viewpoint of improving the reticulation of the transfer film of the present invention, a water-soluble compound represented by the following structural formula 1 Polymerizable compound, pentaerythritol tetraacrylate mixture (NK ester A-TMMT manufactured by Shin-Nakamura Chemical Co., Ltd.), mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM3LM-N Shin-Nakamura Chemical Co., Ltd.) ), Triacrylate (37%), and a mixture of pentaerythritol tetraacrylate and triacrylate (NK ester A-TMM-3L, Shin-Nakamura Chemical Co., Ltd., triacrylate 55%) can be preferably used.

As the photopolymerizable compound used in the resin composition used to form the other optical adjustment member, it has solubility in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms such as methanol and water, It is preferable when an alcohol dispersion of metal oxide particles described below is used in combination with a resin composition used for forming an optical adjustment member that is an aqueous resin composition. Examples of the polymerizable compound having solubility in water or a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water include a monomer having a hydroxyl group, an ethylene oxide or a polypropylene oxide, and a phosphoric acid group in a molecule. Monomers can be used. Examples of polymerizable compounds having solubility in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water include Kayarad RP-1040 (manufactured by Nippon Kayaku Co., Ltd.) and Aronix TO-2349 (manufactured by Toagosei Co., Ltd.) ), Polymerizable monomers A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.), A-GLY-20E (manufactured by Shin-Nakamura Chemical Co., Ltd.) and the like are preferable. Here, that the polymerizable compound has solubility in a mixed solvent of a lower alcohol having 1 to 3 carbon atoms and water means that the polymerizable compound is dissolved in a mixed solvent of alcohol and water by 0.1% by mass or more.
Further, the content of the polymerizable compound is preferably from 0 to 20% by mass, more preferably from 0 to 10% by mass, based on the total mass of the solid content of the resin composition for forming the optical adjustment member. More preferably, it is 0 to 5% by mass.

-Photopolymerization initiator-
Irgacure 2959 or an initiator of the following structural formula 11 is used as a photopolymerization initiator having solubility in water or a mixed solvent of water and a lower alcohol having 1 to 3 carbon atoms, which is used for an optical adjustment member. it can.
Further, the content of the polymerization initiator is preferably from 0 to 5% by mass, more preferably from 0 to 1% by mass, based on the total mass of the solid content of the resin composition for forming the optical adjustment member. More preferably, it is 0 to 0.5% by mass.

-Metal oxide particles-
The resin composition used to form the above-described optical adjustment member may or may not contain particles (preferably metal oxide particles) for the purpose of adjusting the refractive index and light transmittance. However, it is preferable that the resin composition used for forming the high refractive index layer contains metal oxide particles from the viewpoint of controlling the refractive index of the high refractive index layer of the optical adjustment member within the above range. The resin composition used to form the high refractive index layer of the optical adjustment member contains metal oxide particles at an arbitrary ratio depending on the type of the polymer or the polymerizable compound (preferably the photopolymerizable compound) used. be able to. In the resin composition used for forming the high-refractive-index layer, the metal oxide particles are included in an amount of 10 to 95 mass with respect to the total solid content of the resin composition used for forming the high-refractive-index layer. %, More preferably 40 to 95% by mass, particularly preferably 55 to 95% by mass, particularly preferably 62 to 90% by mass, and 65 to 90% by mass. Is even more particularly preferred.
The refractive index of the metal oxide particles is preferably higher than the refractive index of the optical adjustment member that does not contain the metal oxide particles. That is, it is preferable that the above-mentioned metal oxide particles have a higher refractive index than the refractive index of a composition made of a material obtained by removing the particles from the optical adjustment member. Specifically, the high refractive index layer of the optical adjustment member preferably contains particles having a refractive index of 1.50 or more in light having a wavelength of 400 to 750 nm, and particles having a refractive index of 1.55 or more. More preferably, it contains particles having a refractive index of 1.70 or more, particularly preferably 1.90 or more.
Here, that the refractive index in light having a wavelength of 400 to 750 nm is 1.50 or more means that the average refractive index in light having a wavelength in the above range is 1.50 or more, It is not necessary that the refractive index of all light having a wavelength be 1.50 or more. Further, the average refractive index is an average value of the refractive index for light of each wavelength in the above range.

Note that the metal of the metal oxide particles described above also includes semimetals such as B, Si, Ge, As, Sb, and Te.
Examples of the metal oxide particles having high light transmission and a high refractive index include Be, Mg, Ca, Sr, Ba, Sc, Y, La, Ce, Gd, Tb, Dy, Yb, Lu, Ti, Zr, Hf, and Nb. , Mo, W, Zn, B, Al, Si, Ge, Sn, Pb, Sb, Bi, Te, etc., are preferred. Titanium oxide, titanium composite oxide, zinc oxide, zirconium oxide, indium / Tin oxide and antimony / tin oxide are more preferred, titanium oxide, titanium composite oxide and zirconium oxide are more preferred, titanium oxide and zirconium oxide are particularly preferred, and titanium oxide is most preferred. As the titanium oxide, a rutile type having a particularly high refractive index is preferable. The surface of these metal oxide particles can be treated with an organic material for imparting dispersion stability.

  In light of transparency of the optical adjustment member, the average primary particle diameter of the metal oxide particles is preferably 1 to 200 nm, and particularly preferably 3 to 80 nm. Here, the average primary particle diameter of particles refers to the arithmetic average of the particle diameters of 200 arbitrary particles measured with an electron microscope. When the shape of the particles is not spherical, the longest side is defined as the diameter.

Further, one kind of the above-mentioned metal oxide particles may be used alone, or two or more kinds may be used in combination.
In the present invention, it is preferable that the optical adjustment member has at least one of ZrO ₂ particles, Nb ₂ O ₅ particles, and TiO ₂ particles from the viewpoint of controlling the refractive index within the range of the refractive index of the optical adjustment member. _Two particles or Nb ₂ O ₅ particles are more preferred.
The high refractive index layer of the optical adjustment member described above may or may not include metal oxide particles, but may include metal oxide particles, and the refractive index of the optical adjustment member falls within the above range. It is preferable from the viewpoint of controlling the rate. The high refractive index layer of the above-described optical adjustment member may contain metal oxide particles at an arbitrary ratio depending on the type of the polymer or the polymerizable compound used. In the high refractive index layer of the optical adjustment member, the metal oxide particles are preferably contained in an amount of 10 to 95% by mass based on the solid content of the high refractive index layer of the optical adjustment member. The content is more preferably 95% by mass, particularly preferably 62 to 90% by mass, and particularly preferably 65 to 90% by mass.
On the other hand, the low refractive index layer of the optical adjustment member may or may not contain metal oxide particles. , 0 to 35% by mass, more preferably 0 to 10% by mass, and particularly preferably 0 to 35% by mass. It is preferable that the low refractive index layer of the optical adjustment member does not contain metal oxide particles, but the case where metal oxide particles are also included in the present invention. When the low refractive index layer of the optical adjustment member contains metal oxide particles, examples of the type of metal oxide particles include ZrO ₂ particles, Nb ₂ O ₅ particles, and TiO ₂ particles.
The method for measuring the contents of the metal oxide particles in the transparent protective layer and the optical adjustment member in the composite with a transparent electrode of the present invention is as follows.
After cutting the cross section of the composite with a transparent electrode, the cross section is observed with a TEM (Transmission Electron Microscope). The ratio of the area occupied by the metal oxide particles in the film cross-sectional area of the optical adjustment member (or the transparent protective layer) is measured at any three points in the layer, and the average value is defined as a volume fraction (VR). Regard it.
The volume fraction (VR) and the weight fraction (WR) are converted by the following equation to calculate the weight fraction (weight) of the metal oxide particles in the optical adjustment member (or the transparent protective layer). calculate.
WR = D * VR / (1.1 * (1-VR) + D * VR)
D: Specific gravity of metal oxide particles It can be calculated as D = 4.0 when the metal oxide particles are titanium oxide, and D = 6.0 when the metal oxide particles are zirconium oxide.

-Metal oxidation inhibitor-
It is preferable that the resin composition used for forming the above-described optical adjustment member contains a metal oxidation inhibitor. When the optical adjustment member contains a metal oxidation inhibitor, when the optical adjustment member is laminated on a base material (the base material preferably includes a transparent electrode pattern and a metal wiring portion, etc.), It becomes possible to perform a surface treatment on a metal wiring portion that is in direct contact. It is considered that the protective property of the metal wiring portion provided by performing the surface treatment is effective even after the optical adjustment member (and the transparent protective layer) is removed.
The metal oxidation inhibitor used in the present invention is preferably a compound having an aromatic ring containing a nitrogen atom in the molecule.
Further, as the metal oxidation inhibitor used in the present invention, the aromatic ring containing a nitrogen atom is preferably an imidazole ring, a triazole ring, a tetrazole ring, a thiadiazole ring, or a condensed ring thereof and another aromatic ring. It is preferably at least one ring selected from the group consisting of the above, and more preferably, the aromatic ring containing a nitrogen atom is an imidazole ring or a condensed ring of an imidazole ring and another aromatic ring.
The other aromatic ring may be a homocyclic ring or a heterocyclic ring, but is preferably a monocyclic ring, more preferably a benzene ring or a naphthalene ring, and further preferably a benzene ring.
As the metal oxidation inhibitor, imidazole, benzimidazole, tetrazole, mercaptothiadiazole and benzotriazole are preferred, and imidazole, benzimidazole and benzotriazole are more preferred.
Further, the content of the metal oxidation inhibitor is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass based on the total mass of the low refractive index layer or the high refractive index layer of the optical adjustment member. Is more preferable, and 1 to 5% by mass is further preferable.

(Dry)
Preferred ranges of the detailed conditions of the heating and drying steps are shown below.
The method of heating and drying can be carried out by passing through a furnace equipped with a heating device or by blowing air. The heating and drying conditions may be appropriately set according to the organic solvent used and the like, and examples thereof include a method of heating to a temperature of 40 to 150 ° C.
When the transparent protective layer and the optical adjustment member are formed, it is particularly preferable to heat at a drying temperature of 100 to 130 ° C, and it is more preferable to heat to a temperature of 110 to 120 ° C.
The composition after heating and drying preferably has a moisture content on a wet basis of 5% by mass or less, more preferably 3% by mass or less, even more preferably 1% by mass or less.

  Further, the method for producing a transfer film preferably includes a step of generating an acid group by volatilizing ammonia from an ammonium salt of a monomer having an acid group or an ammonium salt of a resin having an acid group. From the ammonium salt of a monomer having an acid group or the ammonium salt of a resin having an acid group, a step of generating an acid group by volatilizing ammonia is a step of heating the applied aqueous resin composition. Preferably, there is.

<Other steps>
The method of manufacturing the transfer film may include a step of forming a thermoplastic resin layer before forming the transparent protective layer on the temporary support.

  After the step of forming the thermoplastic resin layer, a step of forming an intermediate layer between the thermoplastic resin layer and the transparent protective layer may be included. When a transfer film having an intermediate layer is formed, a dissolving solution (a coating solution for a thermoplastic resin layer) in which an additive is dissolved together with a thermoplastic organic polymer is applied onto a temporary support, dried, and dried. After the thermoplastic resin layer is provided, a preparation liquid (coating liquid for an intermediate layer) prepared by adding a resin or an additive to a solvent that does not dissolve the thermoplastic resin layer is applied onto the thermoplastic resin layer, and dried, and the intermediate liquid is dried. It is preferred to stack the layers. It is preferable that a photosensitive resin layer coating solution prepared using a solvent that does not dissolve the intermediate layer is further applied on the intermediate layer, and dried to laminate the photosensitive resin layer.

  Other manufacturing methods such as the step of forming a protective film on the optical adjustment member described above can adopt the method for producing a photosensitive transfer material described in paragraphs 0094 to 0098 of JP-A-2006-259138. .

<Use of transfer film>
The transfer film of the present invention is preferably a dry resist film. In the present specification, a dry resist refers to a product in which a transfer film is in a film form.
The transfer film of the present invention is preferably used for a transparent insulating layer or a transparent protective layer of a capacitance-type input device. The transfer film of the present invention can be preferably used as a transfer material for forming a laminated pattern of an optical adjustment member and a transparent protective layer on a transparent electrode pattern by a photolithography method.

[Capacitive input device]
The capacitance-type input device of the present invention includes the composite with a transparent electrode of the present invention.
The capacitance-type input device is manufactured by using the transfer film of the present invention and laminating the above-described optical adjustment member and the above-described transparent protective layer of the transfer film on the substrate including the transparent electrode pattern in this order. Preferably, an optical adjustment member and a transparent protective layer disposed adjacent to the above-described optical adjustment member are transferred from the transfer film of the present invention onto a transparent electrode pattern of a capacitance-type input device and produced. More preferably, it is performed.
In the capacitance-type input device of the present invention, it is preferable that the transparent protective layer and the optical adjustment member transferred from the transfer film of the present invention are simultaneously cured, and the transparent protective layer and the optical adjustment member are simultaneously pattern-cured. Is more preferred. In addition, when simultaneously curing the transparent protective layer and the optical adjustment member transferred from the transfer film of the present invention, it is preferable not to peel the temporary support from the transfer film of the present invention.
More preferably, the capacitive input device of the present invention develops and removes the uncured portions of the transparent protective layer and the optical adjustment member that are transferred from the transfer film of the present invention and are simultaneously pattern-cured. In addition, after simultaneously curing the transparent protective layer and the optical adjustment member transferred from the transfer film of the present invention, it is preferable to peel the temporary support from the transfer film of the present invention before developing. Since the capacitance type input device of the present invention needs to be connected to the flexible wiring formed on the polyimide film at the terminal portion of the routing wiring, it is not covered with the transparent protective layer (and the optical adjustment member). Is preferred.
The mode is shown in FIG. FIG. 13 shows a capacitance-type input device having the following configuration, including a routing line (another conductive element 6) of the transparent electrode pattern and a terminal portion 31 of the routing line.
Since the transparent protective layer on the terminal portion 31 of the wiring is an uncured portion (unexposed portion), it is removed by development, and the terminal portion 31 of the wiring is exposed.
The specific modes of exposure and development are shown in FIGS. FIG. 14 shows a state before a transfer film 30 of the present invention having a transparent protective layer and an optical adjustment member is laminated on a transparent electrode pattern of a capacitance-type input device by lamination and cured by exposure or the like. In the case of using photolithography, that is, in the case of curing by exposure, the transparent protective layer having the shape shown in FIG. 15 and the cured portion (exposed portion) 33 of the optical adjustment member are subjected to pattern exposure and unexposed portions using a mask. It can be obtained by developing. Specifically, in FIG. 15, the transparent protective layer and the opening 34 corresponding to the terminal portion of the routing wiring as the uncured portion of the optical adjustment member and the outside of the outline of the frame portion of the capacitive input device protrude. The end portion of the transfer film of the present invention having the transparent protective layer and the optical adjustment member is removed, and the transparent protection layer and the cured portion of the optical adjustment member for not covering the terminal portion (extraction wiring portion) of the routing wiring ( Desired pattern) is obtained.
As a result, the flexible wiring formed on the polyimide film can be directly connected to the terminal 31 of the routing wiring, whereby the signal of the sensor can be sent to the electric circuit.
Hereinafter, preferred embodiments of the capacitance-type input device of the present invention will be described in detail.

The capacitance-type input device of the present invention includes at least a substrate (corresponding to the aforementioned substrate in the composite with a transparent electrode of the present invention; also referred to as a front plate) and a non-contact surface side of the aforementioned substrate. It is preferable to have the following components (3) to (5), (7) and (8), and to have the composite with a transparent electrode of the present invention.
(3) a plurality of first transparent electrode patterns formed by extending a plurality of pad portions in a first direction via the connection portions;
(4) a plurality of second electrode patterns which are electrically insulated from the first transparent electrode pattern and include a plurality of pad portions formed so as to extend in a direction intersecting the first direction;
(5) an insulating layer for electrically insulating the first transparent electrode pattern and the second electrode pattern;
(7) an optical adjustment member formed so as to cover all or a part of the above-mentioned elements (3) to (5);
(8) A transparent protective layer formed adjacent to and covers the above-mentioned element (7).
Here, the above-mentioned (7) optical adjustment member corresponds to the above-mentioned optical adjustment member in the composite with a transparent electrode of the present invention. Further, the above-mentioned (8) transparent protective layer corresponds to the above-mentioned transparent protective layer in the composite with a transparent electrode of the present invention. The above-mentioned transparent protective layer is preferably a so-called transparent protective layer in a generally known capacitance-type input device.

In the capacitance type input device of the present invention, the above-mentioned (4) second electrode pattern may or may not be a transparent electrode pattern, but is preferably a transparent electrode pattern.
The capacitance-type input device of the present invention further includes: (6) the first transparent electrode, which is electrically connected to at least one of the first transparent electrode pattern and the second electrode pattern. It may have a conductive element different from the pattern and the aforementioned second electrode pattern.
Here, when the above (4) second electrode pattern is not a transparent electrode pattern and the above (6) does not have another conductive element, the above (3) first transparent electrode pattern is This corresponds to the transparent electrode pattern in the composite with a transparent electrode of the present invention.
When the above (4) second electrode pattern is a transparent electrode pattern and the above (6) does not have another conductive element, the above (3) the first transparent electrode pattern and the above (4) At least one of the second electrode patterns corresponds to the transparent electrode pattern in the composite with a transparent electrode of the present invention.
In the case where the above-mentioned (4) second electrode pattern is not a transparent electrode pattern but has the above-mentioned (6) another conductive element, the above-mentioned (3) the first transparent electrode pattern and the above-mentioned (6) At least one of the conductive elements corresponds to the transparent electrode pattern in the composite with a transparent electrode of the present invention.
When the above (4) second electrode pattern is a transparent electrode pattern and the above (6) has another conductive element, the above (3) first transparent electrode pattern, the above (4) At least one of the second electrode pattern and the another conductive element (6) corresponds to a transparent electrode pattern in the composite with a transparent electrode of the present invention.

  The capacitance type input device of the present invention further comprises (2) a transparent film between the above-mentioned (3) first transparent electrode pattern and the above-mentioned base material, and the above-mentioned (4) second electrode pattern and the above-mentioned second electrode pattern. Or between the above-mentioned substrates or between (6) another conductive element and the above-mentioned substrate. Here, it is preferable that the above-mentioned (2) transparent film corresponds to the transparent film in the composite with a transparent electrode of the present invention.

It is preferable that the capacitance-type input device of the present invention further has (1) a mask layer and / or a decoration layer as necessary. The above-mentioned mask layer is also provided as a black frame around a region touched by a finger or a touch pen or the like so as to make the routing wiring of the transparent electrode pattern invisible from the contact side or to decorate. The above-described decorative layer is provided as a frame around a region touched by a finger or a touch pen or the like for decoration, and for example, it is preferable to provide a white decorative layer.
The above-mentioned (1) mask layer and / or decorative layer is formed between the above-mentioned (2) transparent film and the above-mentioned base material, the above-mentioned (3) between the first transparent electrode pattern and the above-mentioned base material, It is preferable to have (4) between the second transparent electrode pattern and the above-mentioned base material, or (6) between another conductive element and the above-mentioned base material. It is more preferable that the above-mentioned (1) mask layer and / or decorative layer be provided adjacent to the above-mentioned base material.

  The capacitance-type input device of the present invention includes the above-described optical adjustment member disposed adjacent to the transparent electrode pattern and the adjacent optical adjustment member even when including various members. By including the above-mentioned transparent protective layer, the transparent electrode pattern can be made inconspicuous, and the problem of the concealability of the transparent electrode pattern can be improved.

<Configuration of capacitive input device>
First, a preferred configuration of the capacitance-type input device of the present invention will be described together with a method of manufacturing each member constituting the device. FIG. 1 is a cross-sectional view showing a preferred configuration of the capacitance-type input device of the present invention. In FIG. 1, the capacitance-type input device 10 includes a substrate 1, a mask layer 2, a transparent film 11 having a refractive index of 1.46 to 1.58, and a first transparent electrode pattern (shown in FIG. It comprises a connection portion 3b) of the first transparent electrode pattern, a second transparent electrode pattern 4, an insulating layer 5, another conductive element 6, an optical adjustment member 12, and a transparent protective layer 7. Are shown.
Similarly, FIG. 9 showing an XY cross section in FIG. 3 to be described later is also a cross-sectional view showing a preferable configuration of the capacitive input device of the present invention. In FIG. 9, the capacitance-type input device 10 includes a substrate 1, a transparent film 11 having a refractive index of 1.46 to 1.58, and a first transparent electrode pattern (the first transparent electrode is shown in the drawing). The embodiment includes a pad portion 3a) of the pattern, a second transparent electrode pattern 4, an optical adjustment member 12, and a transparent protective layer 7.

  For the substrate 1, the materials listed as the material for the transparent electrode pattern in the composite with a transparent electrode of the present invention can be used. In FIG. 1, the side of the substrate 1 on which the respective elements are provided is referred to as a non-contact surface side. In the capacitance type input device 10 of the present invention, an input is performed by bringing a finger or the like into contact with the contact surface (the surface opposite to the non-contact surface) of the base material 1.

Further, a mask layer 2 is provided on the non-contact surface of the substrate 1. The mask layer 2 is a frame-shaped pattern around the display area formed on the non-contact surface side of the touch panel base material, and is formed so as to make the lead wiring and the like invisible.
As shown in FIG. 2, the capacitive input device 10 of the present invention is provided with a mask layer 2 so as to cover a partial area of the substrate 1 (an area other than the input surface in FIG. 2). I have. Furthermore, the base material 1 can be provided with an opening 8 in a part as shown in FIG. The opening 8 can be provided with a mechanical switch of a pressing type.

  In FIG. 1, a plurality of first transparent electrode patterns 3 (shown in FIG. 1) formed on a non-contact surface of the base material 1 by forming a plurality of pad portions extending in a first direction via connection portions. The connection portion 3b) of the first transparent electrode pattern is electrically insulated from the first transparent electrode pattern 3, and the plurality of connection portions are formed so as to extend in a direction intersecting the first direction. A plurality of second transparent electrode patterns 4 each composed of a pad portion, and an insulating layer 5 for electrically insulating the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed. The first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 described above use the materials listed as the material of the transparent electrode pattern in the composite with a transparent electrode of the present invention. And an ITO film is preferable.

At least one of the first transparent electrode pattern 3 and the second transparent electrode pattern 4 extends over both the non-contact surface of the substrate 1 and the surface of the mask layer 2 opposite to the substrate 1. Can be installed. FIG. 1 shows a state in which the second transparent electrode pattern 4 is provided over both the non-contact surface of the substrate 1 and the surface of the mask layer 2 on the side opposite to the substrate 1. ing.
As described above, even when the photosensitive film is laminated over the mask layer having a certain thickness and the non-contact surface (the back surface of the contact surface) of the base material, the photosensitive film having a specific layer configuration described below is used. By using this, laminating can be performed in a simple process without generating bubbles at the boundary of the mask portion without using expensive equipment such as a vacuum laminator.

The first transparent electrode pattern 3 and the second transparent electrode pattern 4 will be described with reference to FIG. FIG. 3 is an explanatory diagram showing an example of the first transparent electrode pattern and the second transparent electrode pattern in the present invention. As shown in FIG. 3, the first transparent electrode pattern 3 is formed such that the pad portion 3a extends in the first direction C via the connection portion 3b. Further, the second transparent electrode pattern 4 is electrically insulated from the first transparent electrode pattern 3 by the insulating layer 5 and extends in a direction crossing the first direction C (the second direction D in FIG. 3). ) Is formed by a plurality of pad portions formed so as to extend. Here, when the first transparent electrode pattern 3 is formed, the above-described pad portion 3a and the connection portion 3b may be integrally formed, or only the connection portion 3b may be formed, and the pad portion 3a and the second portion may be formed. The transparent electrode pattern 4 may be integrally formed (patterned). When the pad portion 3a and the second transparent electrode pattern 4 are integrally formed (patterned), as shown in FIG. 3, a part of the connection portion 3b is connected to a part of the pad portion 3a, and the insulating layer is formed. 5, the respective layers are formed so that the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are electrically insulated.
The region where the first transparent electrode pattern 3, the second transparent electrode pattern 4, and another conductive element 6 in FIG. 3 are not formed corresponds to the non-pattern region 22 in the composite with a transparent electrode of the present invention. I do.

In FIG. 1, another conductive element 6 is provided on the surface of the mask layer 2 opposite to the substrate 1. Another conductive element 6 electrically connects at least one of the first transparent electrode pattern 3 (the connection portion 3b of the first transparent electrode pattern shown in FIG. 1) and the second transparent electrode pattern 4. And is a different element from the first transparent electrode pattern 3 and the second transparent electrode pattern 4.
FIG. 1 shows an embodiment in which another conductive element 6 is connected to the second transparent electrode pattern 4.

  In FIG. 1, a transparent protective layer 7 is provided so as to cover all the components. The transparent protective layer 7 may be configured to cover only a part of each component. The insulating layer 5 and the transparent protective layer 7 may be made of the same material or different materials. As a material for forming the insulating layer 5, those listed as materials for the transparent protective layer or the optical adjustment member in the composite with a transparent electrode of the present invention can be preferably used.

<Manufacturing method of capacitive input device>
Examples of the mode formed in the process of manufacturing the capacitance type input device of the present invention include the modes shown in FIGS. FIG. 4 is a top view illustrating an example of the base material 1 in which the openings 8 are formed. FIG. 5 is a top view illustrating an example of the base material on which the mask layer 2 is formed. FIG. 6 is a top view illustrating an example of the base material on which the first transparent electrode pattern 3 is formed. FIG. 7 is a top view illustrating an example of the base material on which the first transparent electrode pattern 3 and the second transparent electrode pattern 4 are formed. FIG. 8 is a top view showing an example of a base material on which a conductive element 6 different from the first transparent electrode pattern and the second transparent electrode pattern is formed. These show examples that embody the following description, and the scope of the present invention is not limited to these drawings.

  In the method of manufacturing the capacitance-type input device, when the above-described optical adjustment member 12 and the above-described transparent protective layer 7 are formed, the above-described substrate on which each element is arbitrarily formed using the transfer film of the present invention. It can be formed by transferring the above-mentioned optical adjustment member and the above-mentioned transparent protective layer to the surface of the first member.

In the method of manufacturing the capacitance-type input device, at least one of the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, and another conductive element 6 is used. Is preferably formed using the above-described photosensitive film having a temporary support and a photocurable resin layer in this order.
Using the transfer film of the present invention or the photosensitive film described above, the above-described components (the mask layer 2, the first transparent electrode pattern 3, the second transparent electrode pattern 4, the insulating layer 5, and another conductive When at least one element of the conductive element 6 is formed, the resist component does not leak and / or protrude from the opening even in the substrate having the opening, and in particular, it is necessary to form a light-shielding pattern right above the boundary line of the edge of the substrate. There is no leakage and / or protruding of the resist component from the edge of the base material in the mask layer having the defect. Therefore, a thinner and lighter touch panel can be manufactured by a simple process without contaminating the non-contact surface side of the base material.

  Forming a permanent material such as a mask layer, an insulating layer, a first transparent electrode pattern, a second transparent electrode pattern and a conductive element when using a conductive photocurable resin layer using the above-described photosensitive film. In this case, the photosensitive film may be subjected to pattern exposure as needed after being laminated on the substrate. The above-mentioned photosensitive film may be a negative type material or a positive type material. When the above-mentioned photosensitive film is a negative type material, a pattern can be obtained by developing and removing the non-exposed portion and, when the photosensitive film is a positive type material, the exposed portion. In the development, the thermoplastic resin layer and the photocurable resin layer may be removed by development with different liquids or may be removed with the same liquid. If necessary, known developing equipment such as a brush and a high-pressure jet may be combined. After development, post-exposure and post-bake may be performed as necessary.

(Photosensitive film)
The above-mentioned photosensitive film other than the transfer film of the present invention, which is preferably used when manufacturing the capacitance type input device of the present invention, will be described. The above-mentioned photosensitive film preferably has a temporary base and a photocurable resin layer, and preferably has a thermoplastic resin layer between the temporary base and the photocurable resin layer. When a mask layer or the like is formed using a photosensitive film having the above-described thermoplastic resin layer, bubbles are less likely to be generated in an element formed by transferring the photocurable resin layer, and image unevenness or the like occurs on an image display device. It hardly occurs, and excellent display characteristics can be obtained.
The above-mentioned photosensitive film may be a negative type material or a positive type material.

-Layers other than photocurable resin layer, manufacturing method-
As the above-mentioned temporary base material and the above-mentioned thermoplastic resin layer in the above-mentioned photosensitive film, the same temporary support and the same thermoplastic resin layer as those used for the transfer film of the present invention are used. Can be used. Also, as the method for producing the above-mentioned photosensitive film, the same method as the method for producing the transfer film of the present invention can be used.

-Photocurable resin layer-
In the above-mentioned photosensitive film, an additive is added to the photocurable resin layer depending on the use. That is, when the above-described photosensitive film is used for forming the mask layer, the photocurable resin layer contains a coloring agent. When the photosensitive film has a conductive photocurable resin layer, the photocurable resin layer contains conductive fibers and the like.

The photocurable resin layer of the photosensitive film may be a negative type material or a positive type material.
When the photocurable resin layer of the photosensitive film is a negative-type material, the photocurable resin layer preferably contains an alkali-soluble resin, a polymerizable compound, and a polymerization initiator. Further, a conductive fiber, a colorant, other additives, and the like are used, and the present invention is not limited thereto.
The materials of the photocurable resin layer, the mask layer using a photosensitive film, the formation of an insulating layer, the first and second transparent electrode patterns using a photosensitive film, and the formation of another conductive element are described in JP-A-2014-178922. Publications [0226] to [0255] can be used, and the contents of this publication are incorporated herein.

<Image display device>
The capacitance-type input device of the present invention and an image display device including the capacitance-type input device as constituent elements are described in “Latest Touch Panel Technology” (Techno Times, Inc., issued on July 6, 2009), Mitani The configuration disclosed in Yuji supervision, "Touch panel technology and development", CMC Publishing (2004, 12), FPD International 2009 Forum T-11 lecture textbook, Cypress Semiconductor Corporation Application Note AN2292, etc. can be applied. .

Hereinafter, the present invention will be described more specifically with reference to examples. Materials, usage amounts, ratios, processing contents, processing procedures, and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples described below. Unless otherwise specified, “parts” and “%” are based on mass.
Example 8 is a reference example.

[Examples 1, 2, 4, 5 and Comparative Examples 3 to 5]
<Preparation of transfer film>
(Preparation of materials for transparent protective layer and optical adjustment member)
As shown in the following table, a material A1 as a coating solution for a transparent protective layer was prepared.

  Next, materials B1 to B5 were prepared as shown in the table below.

Next, materials C1 to C3 were prepared as shown in the table below.

(Preparation of transfer film)
On a temporary support, which is a polyethylene terephthalate film, the material A1 for a transparent protective layer was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below, and applied. A transparent protective layer was formed.
After evaporating the solvent in a drying zone at 120 ° C., the thickness of the film obtained by drying the material described in Table 6 among the materials B1, B2, B3, or B5 using a slit-shaped nozzle is as shown in Table 6 below. The coating amount was adjusted so as to obtain a value, and the second layer was formed from the transparent electrode side of the optical adjustment member.
After evaporating the solvent in the drying zone at 120 ° C., the thickness of the film obtained by drying the material described in Table 6 among the materials C1, C2, or C3 using the slit-shaped nozzle has a value shown in Table 6 below. As described above, the coating amount was adjusted and applied to form the first layer of the optical adjustment member from the transparent electrode side.
The obtained transfer film was dried in a drying zone at 120 ° C. to produce transfer films of Examples 1 to 5 and Comparative Examples 2 to 5.

(Measurement of refractive index and thickness of each layer)
As a method of measuring the refractive index and the thickness, there are a method of calculating from a spectral reflectance spectrum by fitting with a theoretical value, a method of obtaining by an ellipsometry method, and the like. In each example and comparative example, the refractive index and thickness of each layer were calculated from the spectral reflectance spectrum. As a measuring device, a reflection spectral thickness meter FE-3000 (manufactured by Otsuka Electronics Co., Ltd.) was used.
(1) PT100, which is a black polyethylene terephthalate (PET) material, is provided on one surface of the temporary support used in each of the examples and comparative examples via a transparent adhesive tape (trade name: OCA tape 8171CL: manufactured by 3M). A laminate to which NB (manufactured by Lintec Corporation) was adhered was produced. The reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the temporary support and the black PET was measured using a reflection spectral film thickness meter FE-3000, and the refractive index of the temporary support at each wavelength was obtained by calculation.
(2) A transparent adhesive tape (OCA tape 8171CL: manufactured by 3M Co., Ltd.) was applied to the temporary support surface of the sample in which only the transparent protective layer was formed on the temporary support in the same manner as in each example and comparative example. Then, a laminate in which a black PET material was brought into contact was produced. The reflection spectrum (wavelength: 430 to 800 nm) of the laminate of the transparent protective layer, the temporary support, and the black PET was measured using a reflection spectral thickness meter FE-3000, and the FFT (Fast Fourier Transform) method was used. The refractive index of the transparent protective layer and the thickness of the transparent protective layer at each wavelength were determined by a fitting operation using the least square method. At this time, the thickness of the transparent protective layer measured using a transmission electron microscope (TEM: HT7700, Hitachi High-Tech Fielding Co., Ltd.) was used as the initial value of the thickness used in the calculation.
(3) Similarly, a laminate of the temporary support, the transparent protective layer, and the second layer from the transparent electrode side, the temporary support, the transparent protective layer, the second layer from the transparent electrode side, and 1 layer from the transparent electrode side The refractive index and thickness of each layer were calculated while sequentially measuring the reflection spectrum of the layered product obtained by laminating a black PET material to the sample of the layered product up to the first layer.

<Preparation of composite with transparent electrode>
(Formation of transparent film)
A material D shown in Table 4 below was coated on a 50 μm-thick polyethylene terephthalate film used as a base material using a slit-shaped nozzle, dried at about 110 ° C., and irradiated with ultraviolet rays (integrated light amount of 300 mJ / cm ² ). A transparent film having a refractive index of 1.51 and a thickness of 2 μm was formed.

Structural formula (2)

(Formation of transparent electrode pattern)
-Formation of transparent electrode layer-
The film base on which the transparent film is laminated is introduced into a vacuum chamber, and Direct Current (DC) is used using an ITO target (indium: tin = 95: 5 (molar ratio)) having a SnO ₂ content of 10% by mass. ) An ITO thin film having a thickness of 25 nm and a refractive index of 1.9 was formed by magnetron sputtering (conditions: substrate temperature 150 ° C., argon pressure 0.13 Pa, oxygen pressure 0.01 Pa), and a transparent film and a transparent film were formed on the substrate. A film on which an electrode layer was formed was obtained. The surface resistance of the ITO thin film was 80Ω / □ (Ω per square).

-Preparation of photosensitive film E1 for etching-
A coating liquid for a thermoplastic resin layer having the following formulation H1 was applied to a 75 μm-thick polyethylene terephthalate film temporary base material using a slit nozzle and dried. Next, a coating solution for an intermediate layer having the following formulation P1 was applied and dried. Further, a coating liquid for a photocurable resin layer for etching having the following formulation E1 was applied and dried. Thus, on the temporary substrate, a thermoplastic resin layer having a dry film thickness of 15.1 μm, an intermediate layer having a dry film thickness of 1.6 μm, and a photocurable resin layer for etching having a thickness of 2.0 μm were formed. A laminate was obtained, and finally a protective film (12 μm thick polypropylene film) was pressed. Thus, a photosensitive film E1 for etching in which the temporary base material, the thermoplastic resin layer, the intermediate layer, and the photocurable resin layer for etching were integrated was produced.

--- Coating liquid for photocurable resin layer for etching: Formulation E1 ---
-Methyl methacrylate / styrene / methacrylic acid copolymer (copolymer composition (% by mass): 31/40/29, weight average molecular weight 6000)
0, acid value: 163 mgKOH / g): 16 parts by mass, monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
: 5.6 parts by mass, 0.5 mol of tetraethylene oxide monomethacrylate adduct of hexamethylene diisocyanate: 7 parts by mass, cyclohexane dimethanol monoacrylate as a compound having one polymerizable group in the molecule: 2.8 parts by mass・ 2-chloro-N-butylacridone: 0.42 parts by mass. 2,2-bis (orthochlorophenyl) -4,4 ′, 5,5′-tetraphenylbiimidazole: 2.17 parts by mass. Malachite green Oxalate: 0.02 parts by mass. Leuco crystal violet: 0.26 parts by mass. Phenothiazine: 0.013 parts by mass. Surfactant (trade name: Megafac F780F, manufactured by Dainippon Ink Co., Ltd.)
: 0.03 parts by mass, methyl ethyl ketone: 40 parts by mass, 1-methoxy-2-propanol: 20 parts by mass. The viscosity of the coating solution E1 for the photocurable resin layer for etching after removing the solvent at 100 ° C is 2500 Pa · s. Met.

--- Coating solution for thermoplastic resin layer: Formulation H1--
-Methanol: 11.1 parts by weight-Propylene glycol monomethyl ether acetate: 6.36 parts by weight-Methyl ethyl ketone: 52.4 parts by weight-Methyl methacrylate / 2-ethylhexyl acrylate / benzyl methacrylate / methacrylic acid copolymer (copolymer composition ratio) (Molar ratio) = 55/11
. 7 / 4.5 / 28.8, molecular weight = 100,000, Tg ≒ 70 ° C.)
: 5.83 parts by mass · styrene / acrylic acid copolymer (copolymer composition ratio (molar ratio) = 63/37;
Weight average molecular weight = 10000, Tg ≒ 100 ° C.): 13.6 parts by mass / monomer 1 (trade name: BPE-500, manufactured by Shin-Nakamura Chemical Co., Ltd.)
: 9.1 parts by mass Fluorine-based polymer: 0.54 parts by mass The above fluorine-containing _{polymer, C 6 F 13 CH 2 CH} 2 OCOCH = CH 2 40 parts of _{H (OCH (CH 3) CH} 2) 7 OCOCH Is a copolymer of 55 parts of CH _{2 and} 5 parts of H (OCH ₂ CH ₂ ) ₇ OCOCH = CH ₂ , having a weight average molecular weight of 30,000 and a 30% by mass solution of methyl ethyl ketone (trade name: Megafac F780F, Dainippon Japan) Ink Chemical Industry Co., Ltd.)

--- Coating solution for intermediate layer: Formulation P1--
・ Polyvinyl alcohol: 32.2 parts by mass (trade name: PVA205, manufactured by Kuraray Co., Ltd., saponification degree = 88%, polymerization degree 5)
50)
・ Polyvinyl pyrrolidone: 14.9 parts by mass (trade name: K-30, manufactured by ASP Japan Co., Ltd.)
・ Distilled water: 524 parts by mass ・ Methanol: 429 parts by mass

-Patterning of transparent electrode layer-
The film on which the transparent film and the transparent electrode layer are formed on the base material is washed, and the photosensitive film for etching E1 from which the protective film is removed is opposed to the surface of the transparent electrode layer and the surface of the photocurable resin layer for etching. (Base temperature: 130 ° C., rubber roller temperature: 120 ° C., linear pressure: 100 N / cm, transport speed: 2.2 m / min). After peeling off the temporary substrate, the thermoplastic resin layer and the intermediate layer were transferred to the surface of the transparent electrode layer together with the photocurable resin layer for etching. The distance between the surface of the exposure mask (a quartz exposure mask having a transparent electrode pattern) and the photocurable resin layer for etching is set to 200 μm, and the photocurable resin for etching is set via the thermoplastic resin layer and the intermediate layer. The layer was pattern exposed at an exposure of 50 mJ / cm ² (i-line).
Next, a triethanolamine-based developer (containing 30% by mass of triethanolamine, a solution of T-PD2 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) at 100C at 25 ° C was used. Developing for 2 seconds, dissolving the thermoplastic resin layer and the intermediate layer, using a detergent containing surfactant (trade name: T-SD3 (manufactured by FUJIFILM Corporation) diluted 10 times with pure water) The substrate was washed at 33 ° C. for 20 seconds. Pure water is sprayed from the ultra-high pressure cleaning nozzle, the residue on the thermoplastic resin layer is removed with a rotating brush, and post-baking is performed at 130 ° C. for 30 minutes to etch the transparent film and transparent electrode layer on the substrate. A film on which a photocurable resin layer pattern was formed was obtained.
A film in which a transparent film, a transparent electrode layer, and a photocurable resin layer pattern for etching are formed on a substrate is immersed in an etching bath containing an ITO etchant (hydrochloric acid, aqueous potassium chloride solution at a liquid temperature of 30 ° C.). After processing for 2 seconds (etching process), the transparent electrode layer in the exposed area not covered with the photocurable resin layer for etching is dissolved and removed, and a film with a transparent electrode pattern with the photocurable resin layer pattern for etching is removed. Obtained.
Next, the film with the transparent electrode pattern having the photocurable resin layer pattern for etching was coated with a resist stripper (N-methyl-2-pyrrolidone, monoethanolamine, a surfactant (trade name: Surfynol 465, air (Product) (immersion in a resist stripping bath containing a liquid temperature of 45 ° C), treatment for 200 seconds (stripping treatment), removal of the photocurable resin layer for etching, formation of a transparent film and a transparent electrode pattern on the substrate A film was obtained.

(Lamination of optical adjustment member and transparent protective layer)
Using the transfer film of each example and the comparative example in which the protective film was peeled off, the transparent film and the transparent electrode pattern of the film in which the transparent film and the transparent electrode pattern were formed on the substrate, so that the optical adjustment member covered the optical film. The adjusting member, the transparent protective layer, and the temporary support were transferred in this order to obtain a laminate (substrate temperature: 40 ° C., rubber roller temperature: 110 ° C., linear pressure: 3 N / cm, transport speed: 2 m / min).
Then, using a proximity type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the obtained laminate was exposed to an exposure mask (a quartz exposure mask having a pattern for forming an overcoat). The distance from the temporary support was set to 125 μm, and pattern exposure was performed through the temporary support at an exposure amount of 100 mJ / cm ² (i-line). After peeling off the temporary support, the laminate (film substrate) after pattern exposure was washed with a 2% by mass aqueous solution of sodium carbonate at 32 ° C. for 60 seconds. The residue was removed by injecting ultrapure water from the ultrahigh-pressure cleaning nozzle onto the substrate after the cleaning treatment. Subsequently, air on the substrate was removed by blowing air, and post-baking treatment was performed at 145 ° C. for 30 minutes to obtain composites with transparent electrodes of Examples 1, 2, 4, 5, and Comparative Examples 3 to 5. Was. The composites with transparent electrodes of Examples 1, 2, 4, 5 and Comparative Examples 3 to 5 are the base, the transparent film, the transparent electrode pattern, and the low refractive index which is the first layer arranged from the transparent electrode pattern side. This was a composite with a transparent electrode having an optical adjustment member comprising a layer and a high refractive index layer which was the second layer disposed from the transparent electrode pattern side, and a transparent protective layer.

(Measurement of refractive index and thickness of each layer after producing composite with transparent electrode)
In the same manner as the method of calculating the refractive index and thickness of each layer in the state of the transfer film, using a laminate in which one layer is sequentially laminated on the base material, black PET is laminated on the back surface, and the reflection spectral film thickness is obtained. The reflection spectrum was measured using a total meter FE-3000, and the refractive index and thickness of each layer were calculated by calculation.
As a result, the refractive index and thickness of each layer were equivalent to the values calculated for the transfer film.

[Example 3]
A transfer film of Example 3 was produced in the same manner as in the transfer film of Example 1 except that the amount of coating was adjusted so as to be a value shown in Table 6 below.
The composite of Example 1 except that the transparent electrode layer was directly formed on a 50 μm-thick polyethylene terephthalate film used as a substrate and the transfer film of Example 3 was used instead of the transfer film of Example 1 A composite with a transparent electrode of Example 3 was produced in the same manner as the production.

[Example 6]
On a temporary support, which is a polyethylene terephthalate film, the material A1 for a transparent protective layer was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below, and applied. A transparent protective layer was formed.
After evaporating the solvent in a drying zone at 120 ° C., the material B2 was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below. Of these, the fourth layer from the transparent electrode side was formed.
After evaporating the solvent in a drying zone at 120 ° C., the material C2 was dried using a slit nozzle, and the coating amount was adjusted so that the thickness of the film became the value shown in Table 6 below. Of these, the third layer from the transparent electrode side was formed.
After evaporating the solvent in a drying zone at 120 ° C., the material B4 was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below, and the coating was performed. Of these, the second layer from the transparent electrode side was formed.
After evaporating the solvent in a drying zone at 120 ° C., the material C2 was dried using a slit nozzle, and the coating amount was adjusted so that the thickness of the film became the value shown in Table 6 below. The first layer from the transparent electrode side was formed.
The obtained transfer film was dried in a drying zone at 120 ° C. to prepare a transfer film of Example 6.
In the transfer film of Example 6, in the method for measuring the refractive index and thickness of each layer of the transfer film of Example 1, only the temporary support, the laminate up to the transparent protective layer, and the laminate up to the fourth layer from the transparent electrode side A black PET material was attached to a sample of a laminate, a laminate from the transparent electrode side to the third layer, a laminate from the transparent electrode side to the second layer, and a laminate from the transparent electrode side to the first layer. The refractive index and thickness of each layer were calculated while measuring the reflection spectrum of the laminate in order.
A composite with a transparent electrode of Example 6 was produced in the same manner as in the production of the composite with a transparent electrode of Example 1 except that the transfer film of Example 6 was used instead of the transfer film of Example 1.

[Example 7]
On a temporary support, which is a polyethylene terephthalate film, the material A1 for a transparent protective layer was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below, and applied. A transparent protective layer was formed. The obtained transfer film was dried in a drying zone at 120 ° C. to prepare a transfer film for laminating a transparent protective layer.
On the transparent film and the transparent electrode pattern of the film in which the transparent film and the transparent electrode pattern were formed on the base material produced in the same manner as in Example 1, 1 The SiOx film (x: 2.0, refractive index 1.46) which is the second layer (low refractive index layer), and Y which is the second layer (high refractive index layer) from the side of the transparent electrode pattern having a thickness of 21 nm. _Two layers of ₂ O ₃ films (refractive index: 1.80) were sequentially formed to provide an optical adjustment member.
The transparent protective layer and the temporary support were transferred from a transfer film for laminating the transparent protective layer produced using the material A1 on the optical adjustment member composed of the formed low refractive index layer and high refractive index layer ( Base material temperature: 40 ° C, rubber roller temperature 110 ° C, linear pressure 3 N / cm, transport speed 2 m / min).
After that, using a proximity-type exposure machine (manufactured by Hitachi High-Tech Electronics Engineering Co., Ltd.) having an ultra-high pressure mercury lamp, the surface of the exposure mask (quartz exposure mask having a pattern for forming an overcoat) and the temporary support were used. Was set to 125 μm, and pattern exposure was performed through a temporary support at an exposure amount of 100 mJ / cm ² (i-line). After the temporary support was peeled off, it was washed at 32 ° C. for 2 seconds at 32 ° C. in a 2% aqueous solution of sodium carbonate. The residue was removed by injecting ultrapure water from the ultrahigh-pressure cleaning nozzle onto the substrate after the cleaning treatment. Subsequently, air was blown to remove water on the substrate, and post-baking treatment was performed at 145 ° C. for 30 minutes to produce a composite with a transparent electrode of Example 7.
In the same manner as in Example 1, the refractive index and thickness of each layer after the production of the composite with a transparent electrode were measured. The obtained results are shown in Table 1 below.

Example 8
The thickness of the first layer from the transparent electrode pattern side was changed to the thickness shown in Table 6 below, and the second layer from the transparent electrode pattern side was a ZrO ₂ film (refractive index 2. Except having changed to 10), it carried out similarly to Example 7, and produced the composite with a transparent electrode of Example 8.

[Example 9]
In Example 1, a transparent film was formed in the same manner as in Example 1 except that Material-C shown in Table 5 below was used as the material of the transparent film. A composite with a transparent electrode of Example 9 was produced in the same manner as in Example 1 except that the transparent film formed in Example 9 was used. The transparent film formed in Example 9 was a transparent film having a refractive index of 1.60 and a thickness of 80 nm.

“%” In the table is synonymous with “mass%”. In the description, “wt%” is synonymous with “mass%”.
Equation (3)

[Comparative Example 1]
On a temporary support, which is a polyethylene terephthalate film, the material A1 for a transparent protective layer was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below, and applied. A transparent protective layer was formed.
After evaporating the solvent in a drying zone at 120 ° C., the material B1 was dried using a slit-shaped nozzle, and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below. The first layer from the transparent electrode side was formed.
In the transfer film of Comparative Example 1, in the method for measuring the refractive index and thickness of each layer of the transfer film of Example 1, only the temporary support, the laminate up to the transparent protective layer, and the laminate from the transparent electrode side to the first layer The refractive index and thickness of each layer were calculated while sequentially measuring the reflection spectrum of a laminate in which a black PET material was attached to a body sample.
A composite with a transparent electrode of Comparative Example 1 was produced in the same manner as in the production of the composite with a transparent electrode of Example 1, except that the transfer film of Comparative Example 1 was used instead of the transfer film of Example 1.

[Comparative Example 2]
On a temporary support which is a polyethylene terephthalate film, the material B1 was dried using a slit-shaped nozzle and the coating amount was adjusted such that the thickness of the dried film became the value shown in Table 6 below. The second layer from the transparent electrode side was formed.
After evaporating the solvent in the drying zone at 120 ° C., the material C1 was dried using a slit-shaped nozzle, and the coating amount was adjusted so that the thickness of the film became the value shown in Table 6 below. Among them, the first layer from the transparent electrode side was formed.
The obtained transfer film was dried in a drying zone at 120 ° C. to prepare a transfer film of Comparative Example 2.
A composite with a transparent electrode of Comparative Example 2 was produced in the same manner as in the production of the composite with a transparent electrode of Example 1 except that the transfer film of Comparative Example 2 was used instead of the transfer film of Example 1.

[Comparative Example 6]
In forming the optical adjustment member of Example 7, the thickness of the first layer from the transparent electrode pattern side was changed to the thickness shown in Table 6 below, and the thickness of the second layer from the transparent electrode pattern side was changed to a high refractive index of 21 nm. The film was changed to a Nb ₂ O ₃ film (refractive index 2.33) as a layer, and further, a SiOx film (x) as a third layer (low-refractive index layer) from a transparent electrode pattern side having a thickness of 40 nm using a vacuum evaporation method. : 2.0, refractive index 1.46), Nb ₂ O ₃ film (refractive index 2.33) as the fourth layer (high refractive index layer) from the transparent electrode pattern side having a thickness of 29 nm, transparent electrode having a thickness of 97 nm Five layers of SiOx films (x: 2.0, refractive index 1.46), which are the fifth layer (low refractive index layer) from the pattern side, were sequentially formed to form an optical adjustment member. Otherwise, in the same manner as in the preparation of the composite with a transparent electrode in Example, the composite with a transparent electrode in Comparative Example 6 was prepared.

[Comparative Example 7]
The thickness of the first layer from the transparent electrode pattern side was changed to the thickness shown in Table 6 below, and the second layer from the transparent electrode pattern side was a 7 nm thick Nb ₂ O ₃ film (high refractive index layer) (refractive index). A composite with a transparent electrode of Comparative Example 7 was produced in the same manner as in Example 7, except that the composition was changed to 2.33).

[Evaluation of composite with transparent electrode]
<Hiding properties of transparent electrode pattern>
A composite with a transparent electrode, in which a transparent film, a transparent electrode pattern, an optical adjustment member, and a transparent protective layer are laminated in this order on a base material, and a black PET material are bonded to a transparent adhesive tape (trade name, manufactured by 3M, OCA). A black PET material and a transparent adhesive tape were adjacent to each other via a tape 8171CL), and the transparent adhesive tape and the transparent protective layer were adhered in a laminating order adjacent to each other, thereby producing a light-shielded evaluation substrate.
The transparent electrode pattern concealing property is as follows. In a dark room, using a fluorescent lamp (light source) and a prepared evaluation substrate, light is incident from the substrate surface side of the evaluation substrate, and light is incident from the surface of the substrate on the light incident side. Of the transparent electrode pattern was visually observed obliquely, and the concealability of the transparent electrode pattern was evaluated based on the following evaluation criteria. AA, A, B or C is at a practical level, preferably AA, A or B, more preferably AA or A, and particularly preferably AA. The evaluation results are summarized in Table 6 below.
"Evaluation criteria"
AA: The transparent electrode pattern is not visible at all either visually or with a loupe.
A: The transparent electrode pattern is not visible at all. Observed slightly with a loupe.
B: The transparent electrode pattern is slightly visible but hardly visible.
C: Transparent electrode pattern is visible (not easily understood and practically acceptable).
D: Transparent electrode pattern is visible.
E: The transparent electrode pattern is clearly visible (easy to understand).

<Mura due to optical adjustment member>
Further, in the same visual observation method as the transparent electrode pattern concealing property, light is incident from the substrate surface side of the evaluation substrate, and reflected light from the surface of the substrate on the light incident side is an optical element other than the transparent electrode pattern. It was observed whether unevenness caused by the adjustment member could be visually recognized, and evaluated according to the following evaluation criteria. A, B or C is at a practical level, and is preferably A or B, and more preferably A. The evaluation results are summarized in Table 6 below.
"Evaluation criteria"
A: No unevenness due to the optical adjustment member is seen at all.
B: The unevenness caused by the optical adjustment member is slightly visible but hardly visible.
C: Nonuniformity due to the optical adjustment member is visible, but practically acceptable.
D: Unevenness caused by the optical adjustment member is clearly visible (easy to understand).

<Reflectance of transparent electrode pattern>
In the preparation of the composite with a transparent electrode of each Example and Comparative Example, except that the transparent electrode was not patterned, the transparent electrode for measuring the reflectance in the same manner as in the preparation of the composite with the transparent electrode of each Example and Comparative Example A complex was formed. Using this composite with a transparent electrode for reflectance measurement, a sample was prepared in the same manner as in the evaluation of the transparent electrode pattern concealing property described above. The reflectance of the sample to a D65 light source was measured using a spectrophotometer V-570 (manufactured by JASCO Corporation).
The results are summarized in Table 6 below.

<Pencil hardness>
A pencil hardness evaluation described in JIS (Japanese Industrial Standards) K5400 was performed as an index of scratch resistance. The composite with a transparent electrode of each of Examples and Comparative Examples was conditioned for 1 hour at a temperature of 25 ° C. and a relative humidity of 60%, and then with a 2H test pencil specified in JIS S 6006 under a load of 500 g. An evaluation of n = 7 was performed. A, B, and C are at a practical level, preferably A or B, and particularly preferably A.
"Evaluation criteria"
A: Less than three scratches.
B: 3 or more and less than 5 scratches.
C: 5 or more and less than 6 scratches.
D: There are 6 or more scratches.
The obtained results are shown in Table 6 below.

From Table 6 above, it can be seen that the composite with a transparent electrode of the present invention is excellent in the concealing property of the transparent electrode pattern without using a transparent film having a high refractive index on the substrate side of the transparent electrode pattern, and is caused by the optical adjustment member. It can be seen that the resulting unevenness can be reduced and the pencil hardness is excellent. In addition, the low refractive index layer, the high refractive index layer, and the transparent protective layer of the transfer films of Examples 1 to 6 were all determined to be uncured by the method described in International Publication WO2014 / 084112. It was confirmed based on the unsaturated double bond consumption rate of the heavy bond group being less than 10%.
On the other hand, from Comparative Example 1, it was found that when the optical adjustment member was only the high refractive index layer and the first layer from the transparent electrode pattern side did not have the low refractive index layer, the transparency of the transparent electrode pattern was poor. Was.
From Comparative Example 2, it was found that when no transparent protective layer was provided, the pencil hardness was poor.
From Comparative Example 3, when the refractive index of the first layer from the transparent electrode pattern side as the optical adjustment member is not smaller than the refractive index of the second layer from the transparent electrode pattern side by the value specified in the present invention, the transparent electrode pattern Was found to be inferior in concealment.
From Comparative Example 4, it was found that when the thickness of the low refractive index layer and the high refractive index layer used as the optical adjustment member exceeded the upper limit specified in the present invention, the opacity of the transparent electrode pattern was poor.
From Comparative Example 5, it was found that when the thickness of the low refractive index layer used as the optical adjustment member exceeded the upper limit specified in the present invention, the opacity of the transparent electrode pattern was poor. This Comparative Example 5 is intended to carry out a repetition test of a preferred embodiment disclosed in JP-A-2004-50734. It was also found that the composite with a transparent electrode of Comparative Example 5 had a slightly poor pencil hardness.
From Comparative Examples 6 and 7, when the refractive index of the even-numbered high refractive index layer from the transparent electrode pattern side as the optical adjustment member exceeds the upper limit specified in the present invention, the number of high refractive index layers is two or more. In some cases, the opacity of the transparent electrode pattern was poor, and when the number of high refractive index layers was one, the unevenness due to the optical adjustment member was poor.

Furthermore, when the content of the metal oxide particles in the low refractive index layer or the high refractive index layer of the optical adjustment member of the composite with a transparent electrode of each Example and Comparative Example was measured by the following method, the above Table 2 or 3 was obtained. It was the value described in.
After cutting the cross section of the composite with a transparent electrode, the cross section is observed with a TEM (transmission electron microscope). The ratio of the area occupied by the metal oxide particles in the film cross-sectional area of the low refractive index layer or the high refractive index layer of the optical adjustment member is measured at any three locations in the layer, and the average value is the volume fraction (VR). Is considered.
The volume fraction (VR) and the weight fraction (WR) are converted by the following equation to obtain the weight fraction (WR) of the metal oxide particles in the low refractive index layer or the high refractive index layer of the optical adjustment member. Is calculated.
WR = D * VR / (1.1 * (1-VR) + D * VR)
D: Specific gravity of metal oxide particles It can be calculated as D = 4.0 when the metal oxide particles are titanium oxide, and D = 6.0 when the metal oxide particles are zirconium oxide.
The content of the metal oxide particles of the low refractive index layer or the high refractive index layer of the optical adjustment member of the composite with a transparent electrode of each of the Examples and Comparative Examples is determined from the composition of the low refractive index layer or the high refractive index layer. It can also be calculated.

[Examples 101 to 109]
<Production of image display device (touch panel)>
By bonding the composites with the transparent electrodes of each of the examples manufactured above to the liquid crystal display elements manufactured by the methods described in [0097] to [0119] of JP-A-2009-47936, by a known method. An image display device including the composite with a transparent electrode of each of the examples, which includes a capacitance-type input device as a component, was manufactured.

<Evaluation of the capacitive input device and the image display device>
The capacitance-type input device and the image display device each including the composite with a transparent electrode according to each of the embodiments, the transparent electrode pattern is concealed, unevenness due to an optical adjustment member other than the transparent electrode pattern is reduced, and the pencil hardness is excellent. I understand.
The optical adjustment member and the transparent protective layer were free from defects such as bubbles, and an image display device having excellent display characteristics was obtained.

  The composite with a transparent electrode of the present invention has excellent transparent electrode pattern concealing properties, reduces unevenness due to optical adjustment members other than the transparent electrode pattern, and has excellent pencil hardness, so that it is used for touch panels (especially capacitive input devices). And a material for an image display device having a touch panel (especially a capacitance-type input device) as a constituent element. Since the transfer film of the present invention has photolithographic properties, when a desired pattern is to be formed using the transfer film of the present invention, a pattern can be formed by photolithography, which is more productive than the cutting method.

1 base material 2 mask layer 3 transparent electrode pattern (first transparent electrode pattern)
3a Pad portion 3b Connection portion 4 Transparent electrode pattern (second transparent electrode pattern)
Reference Signs List 5 Insulating layer 6 Another conductive element 7 Transparent protective layer 8 Opening 10 Capacitive input device 11 Transparent film 12 Optical adjustment member 12A Low refractive index layer 12B High refractive index layer 13 Composite with transparent electrode 21 Transparent electrode pattern Area where the optical control member and the transparent protective layer are laminated in this order 22 Non-pattern area α Taper angle 26 Temporary support 29 Protective film 30 Transfer film 31 Terminal part 33 of the routing wiring Transparent protective layer and cured part 34 of the optical control member Opening corresponding to the end of the routing wiring (transparent protective layer and uncured part of optical adjustment member)
C First direction D Second direction

Claims (17)

A composite with a transparent electrode having a substrate, a transparent electrode pattern, an optical adjustment member and a transparent protective layer in this order,
The optical adjustment member has at least one low-refractive-index layer that is an odd-numbered layer disposed from the transparent electrode pattern side and a high-refractive-index layer that is an even-numbered layer disposed from the transparent electrode pattern side. Have each layer,
The difference in the refractive index between the low refractive index layer and the directly adjacent high refractive index layer is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The low refractive index layer has a thickness of 5 to 80 nm,
A composite with a transparent electrode, wherein the high refractive index layer has a thickness of 21 to 80 nm.   The composite with a transparent electrode according to claim 1, wherein the substrate and the transparent electrode pattern are disposed directly or via a transparent film having a refractive index of 1.46 to 1.58.   3. The composite with a transparent electrode according to claim 1, wherein the optical adjustment member has the low refractive index layer and the high refractive index layer one by one. 4.   The composite with a transparent electrode according to any one of claims 1 to 3, wherein the low refractive index layer has a refractive index of 1.25 to 1.53.   The composite with a transparent electrode according to any one of claims 1 to 4, wherein the high refractive index layer has a refractive index of 1.60 to 2.00.   The composite with a transparent electrode according to any one of claims 1 to 5, wherein the high refractive index layer contains 10 to 95% by mass of metal oxide particles.   The composite with a transparent electrode according to any one of claims 1 to 6, wherein the optical adjustment member and the transparent protective layer are formed by transfer.   The composite with a transparent electrode according to any one of claims 1 to 7, wherein the low refractive index layer and the high refractive index layer are transparent resin layers.   The composite with a transparent electrode according to any one of claims 1 to 8, wherein the low refractive index layer, the high refractive index layer, and the transparent protective layer are cured films of a curable transparent resin layer. A temporary support, a transparent protective layer, a transfer film having an optical adjustment member and a protective film in this order,
The optical adjustment member has at least one layer each of a low-refractive-index layer arranged odd-numbered from the protective film side and a high-refractive-index layer arranged even-numbered from the protective film side,
The difference in the refractive index between the low refractive index layer and the directly adjacent high refractive index layer is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
Wherein Ri thickness of the low refractive index layer 5 ～80Nm der,
The thickness of the high refractive index layer is Ru 21~80nm der, transfer film. The low refractive index layer and the high refractive index layer is a curable transparent resin layer containing a polymerizable compound,
The transfer film according to claim 10, wherein the curable transparent resin layer is uncured. On the transparent electrode pattern disposed on the substrate, having a lamination step of laminating the optical adjustment member and the transparent protective layer in this order,
The optical adjustment member has at least one layer each of a low-refractive-index layer disposed at an odd-numbered position from the transparent electrode pattern side and a high-refractive-index layer disposed at an even-numbered position from the transparent electrode pattern side,
The difference in the refractive index between the low refractive index layer and the directly adjacent high refractive index layer is 0.05 or more,
The refractive index of the high refractive index layer is 2.10 or less,
The low refractive index layer has a thickness of 5 to 80 nm,
A method for producing a composite with a transparent electrode, wherein the high refractive index layer has a thickness of 21 to 80 nm.   The method for producing a composite with a transparent electrode according to claim 12, wherein the substrate and the transparent electrode pattern are disposed directly or via a transparent film having a refractive index of 1.46 to 1.58.   The said lamination process is a process of transferring the said optical adjustment member and the said transparent protective layer from the transfer film of Claim 10 or 11 on the said transparent electrode pattern arrange | positioned on the said base material. 14. The method for producing a composite with a transparent electrode according to 12 or 13. The low refractive index layer and the high refractive index layer is a curable transparent resin layer containing a polymerizable compound,
The method for producing a composite with a transparent electrode according to any one of claims 12 to 14, wherein the curable transparent resin layer before being laminated on the transparent electrode pattern is uncured.   A composite with a transparent electrode produced by the method for producing a composite with a transparent electrode according to claim 12.   An electrostatic capacitance-type input device comprising the composite with a transparent electrode according to claim 1.

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